Hey onais,

Please refer below sample.

SQL 

CREATE TABLE TestDemo(Name VARCHAR(50), UrduName NVARCHAR(max))
INSERT INTO TestDemo VALUES('India',N'بھارت')
INSERT INTO TestDemo VALUES('China',N'چین')
INSERT INTO TestDemo VALUES('Australia',N'آسٹریلیا')
INSERT INTO TestDemo VALUES('Nepal',N'نیپال')
SELECT * FROM TestDemo

HTML

<asp:Button ID="Button2" runat="server" Text="Generate Report To PDF" OnClick="ExportToPDf" />

Namespaces

C#

using System.Data;
using System.Data.SqlClient;
using System.Configuration;
using System.IO;
using iTextSharp.text;
using iTextSharp.text.pdf;

VB.Net

Imports iTextSharp.text.pdf
Imports System.Data
Imports System.Data.SqlClient
Imports System.IO
Imports iTextSharp.text

Code

C#

private DataTable GetData()
{
    string constr = ConfigurationManager.ConnectionStrings["constr"].ConnectionString;
    using (SqlConnection con = new SqlConnection(constr))
    {
        using (SqlCommand cmd = new SqlCommand("SELECT * FROM TestDemo", con))
        {
            using (SqlDataAdapter da = new SqlDataAdapter(cmd))
            {
                DataTable dt = new DataTable();
                da.Fill(dt);
                return dt;
            }
        }
    }
}

public void PDF()
{
    DataTable dt = GetData();
    GridView GridView11 = new GridView();
    GridView11.AllowPaging = false;
    GridView11.AutoGenerateColumns = false;
    BoundField boundfield = new BoundField();
    for (int i = 0; i < dt.Columns.Count; i++)
    {
        boundfield.DataField = dt.Columns[i].ColumnName.ToString();
        boundfield.HeaderText = dt.Columns[i].ColumnName.ToString();
        GridView11.Columns.Add(boundfield);
    }
    GridView11.DataSource = dt;
    GridView11.DataBind();
    using (MemoryStream ms = new MemoryStream())
    {
        Document document = new Document(iTextSharp.text.PageSize.A4, 10, 22, 34, 34);
        PdfWriter writer = PdfWriter.GetInstance(document, ms);
        document.Open();
        MemoryStream stream = new MemoryStream();
        document.Add(createFirstTable(dt));
        document.Close();
        writer.Close();
        Response.ContentType = "pdf/application";
        Response.AddHeader("content-disposition", "attachment;filename=First PDF document.pdf");
        Response.OutputStream.Write(ms.GetBuffer(), 0, ms.GetBuffer().Length);
    }
}

public static PdfPTable createFirstTable(DataTable dt)
{
    PdfPTable table = new PdfPTable(dt.Columns.Count);
    BaseFont bf = BaseFont.CreateFont(Environment.GetEnvironmentVariable("windir") + @"\fonts\Arial.ttf", BaseFont.IDENTITY_H, true);
    iTextSharp.text.Font font = new iTextSharp.text.Font(bf, 10, iTextSharp.text.Font.NORMAL);
    for (int j = 0; j < dt.Columns.Count; j++)
    {
        table.AddCell(dt.Columns[j].ToString());
    }
    for (int i = 0; i < dt.Rows.Count; i++)
    {
        for (int k = 0; k < dt.Columns.Count; k++)
        {
            iTextSharp.text.pdf.PdfPCell cell = new iTextSharp.text.pdf.PdfPCell(new Phrase(12, dt.Rows[i][k].ToString(), font));
            cell.RunDirection = PdfWriter.RUN_DIRECTION_RTL;
            table.AddCell(cell);
        }
    }
    return table;
}

protected void ExportToPDf(object sender, EventArgs e)
{
    PDF();
}

public override void VerifyRenderingInServerForm(Control control)
{
    /* Verifies that the control is rendered */
}

VB.Net

Private Function GetData() As DataTable
    Dim constr As String = ConfigurationManager.ConnectionStrings("constr").ConnectionString

    Using con As SqlConnection = New SqlConnection(constr)

        Using cmd As SqlCommand = New SqlCommand("SELECT * FROM TestDemo", con)

            Using da As SqlDataAdapter = New SqlDataAdapter(cmd)
                Dim dt As DataTable = New DataTable()
                da.Fill(dt)
                Return dt
            End Using
        End Using
    End Using
End Function

Public Sub PDF()
    Dim dt As DataTable = GetData()
    Dim GridView11 As GridView = New GridView()
    GridView11.AllowPaging = False
    GridView11.AutoGenerateColumns = False
    Dim boundfield As BoundField = New BoundField()

    For i As Integer = 0 To dt.Columns.Count - 1
        boundfield.DataField = dt.Columns(i).ColumnName.ToString()
        boundfield.HeaderText = dt.Columns(i).ColumnName.ToString()
        GridView11.Columns.Add(boundfield)
    Next

    GridView11.DataSource = dt
    GridView11.DataBind()

    Using ms As MemoryStream = New MemoryStream()
        Dim document As Document = New Document(iTextSharp.text.PageSize.A4, 10, 22, 34, 34)
        Dim writer As PdfWriter = PdfWriter.GetInstance(document, ms)
        document.Open()
        Dim stream As MemoryStream = New MemoryStream()
        document.Add(createFirstTable(dt))
        document.Close()
        writer.Close()
        Response.ContentType = "pdf/application"
        Response.AddHeader("content-disposition", "attachment;filename=First PDF document.pdf")
        Response.OutputStream.Write(ms.GetBuffer(), 0, ms.GetBuffer().Length)
    End Using
End Sub

Public Shared Function createFirstTable(ByVal dt As DataTable) As PdfPTable
    Dim table As PdfPTable = New PdfPTable(dt.Columns.Count)
    Dim bf As BaseFont = BaseFont.CreateFont(Environment.GetEnvironmentVariable("windir") & "\fonts\Arial.ttf", BaseFont.IDENTITY_H, True)
    Dim font As iTextSharp.text.Font = New iTextSharp.text.Font(bf, 10, iTextSharp.text.Font.NORMAL)

    For j As Integer = 0 To dt.Columns.Count - 1
        table.AddCell(dt.Columns(j).ToString())
    Next

    For i As Integer = 0 To dt.Rows.Count - 1

        For k As Integer = 0 To dt.Columns.Count - 1
            Dim cell As iTextSharp.text.pdf.PdfPCell = New iTextSharp.text.pdf.PdfPCell(New Phrase(12, dt.Rows(i)(k).ToString(), font))
            cell.RunDirection = PdfWriter.RUN_DIRECTION_RTL
            table.AddCell(cell)
        Next
    Next

    Return table
End Function

Protected Sub ExportToPDf(ByVal sender As Object, ByVal e As EventArgs)
    PDF()
End Sub

Public Overrides Sub VerifyRenderingInServerForm(ByVal control As Control)
End Sub

Screenshot