Hi Bello,

Check this example. Now please take its reference and correct your code.

For adding images in database i have used below article.

Save (Insert) Image in Database in Windows Application using C# and VB.Net

Namespaces

C#

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

VB.Net

Imports System.Configuration
Imports System.Data
Imports System.Data.SqlClient
Imports System.IO
Imports System.Windows.Forms
Imports iTextSharp.text
Imports iTextSharp.text.pdf

Code

C#

private void Form1_Load(object sender, EventArgs e)
{
    BindDataGridView();
}

private void BindDataGridView()
{
    string conString = ConfigurationManager.ConnectionStrings["constr"].ConnectionString;
    string query = "SELECT Id,Name,Data FROM tblFiles WHERE ContentType = 'image/jpeg'";
    SqlCommand cmd = new SqlCommand(query);
    using (SqlConnection con = new SqlConnection(conString))
    {
        using (SqlDataAdapter sda = new SqlDataAdapter())
        {
            cmd.Connection = con;
            sda.SelectCommand = cmd;
            DataTable dt = new DataTable();
            sda.Fill(dt);
            dataGridView1.DataSource = dt;
            dataGridView1.AutoSizeColumnsMode = DataGridViewAutoSizeColumnsMode.AllCells;
            dataGridView1.AutoSizeRowsMode = DataGridViewAutoSizeRowsMode.AllCells;
        }
    }
}

private void btnExport_Click(object sender, EventArgs e)
{
    //Creating iTextSharp Table from the DataTable data
    PdfPTable pdfTable = new PdfPTable(dataGridView1.ColumnCount);
    pdfTable.DefaultCell.Padding = 3;
    pdfTable.WidthPercentage = 30;
    pdfTable.HorizontalAlignment = Element.ALIGN_LEFT;
    pdfTable.DefaultCell.BorderWidth = 1;

    //Adding Header row
    foreach (DataGridViewColumn column in dataGridView1.Columns)
    {
        PdfPCell cell = new PdfPCell(new Phrase(column.HeaderText));
        cell.BackgroundColor = new iTextSharp.text.BaseColor(240, 240, 240);
        pdfTable.AddCell(cell);
    }

    //Adding DataRow
    foreach (DataGridViewRow row in dataGridView1.Rows)
    {
        string id = row.Cells[0].Value.ToString();
        pdfTable.AddCell(id);
        string name = row.Cells[1].Value.ToString();
        pdfTable.AddCell(name);
        byte[] imageByte = (byte[])row.Cells[2].Value;

        iTextSharp.text.Image myImage = iTextSharp.text.Image.GetInstance(imageByte);

        pdfTable.AddCell(myImage);
    }

    //Exporting to PDF.
    string folderPath = @"D:\\";
    if (!Directory.Exists(folderPath))
    {
        Directory.CreateDirectory(folderPath);
    }
    using (FileStream stream = new FileStream(folderPath + "DataGridViewImageExport.pdf", FileMode.Create))
    {
        Document pdfDoc = new Document(PageSize.A2, 10f, 10f, 10f, 0f);
        PdfWriter.GetInstance(pdfDoc, stream);
        pdfDoc.Open();
        pdfDoc.Add(pdfTable);
        pdfDoc.Close();
        stream.Close();
    }
}

VB.Net

Private Sub Form1_Load(sender As System.Object, e As System.EventArgs) Handles MyBase.Load
    BindDataGridView()
End Sub

Private Sub BindDataGridView()
    Dim conString As String = ConfigurationManager.ConnectionStrings("constr").ConnectionString
    Dim query As String = "SELECT Id,Name,Data FROM tblFiles WHERE ContentType = 'image/jpeg'"
    Dim cmd As SqlCommand = New SqlCommand(query)
    Using con As SqlConnection = New SqlConnection(conString)
        Using sda As SqlDataAdapter = New SqlDataAdapter()
            cmd.Connection = con
            sda.SelectCommand = cmd
            Dim dt As DataTable = New DataTable()
            sda.Fill(dt)
            dataGridView1.DataSource = dt
            dataGridView1.AutoSizeColumnsMode = DataGridViewAutoSizeColumnsMode.AllCells
            dataGridView1.AutoSizeRowsMode = DataGridViewAutoSizeRowsMode.AllCells
        End Using
    End Using
End Sub

Private Sub btnExport_Click(ByVal sender As Object, ByVal e As EventArgs) Handles btnExport.Click
    Dim pdfTable As PdfPTable = New PdfPTable(dataGridView1.ColumnCount)
    pdfTable.DefaultCell.Padding = 3
    pdfTable.WidthPercentage = 30
    pdfTable.HorizontalAlignment = Element.ALIGN_LEFT
    pdfTable.DefaultCell.BorderWidth = 1

    For Each column As DataGridViewColumn In dataGridView1.Columns
        Dim cell As PdfPCell = New PdfPCell(New Phrase(column.HeaderText))
        cell.BackgroundColor = New iTextSharp.text.BaseColor(240, 240, 240)
        pdfTable.AddCell(cell)
    Next

    For Each row As DataGridViewRow In dataGridView1.Rows
        Dim id As String = row.Cells(0).Value.ToString()
        pdfTable.AddCell(id)
        Dim name As String = row.Cells(1).Value.ToString()
        pdfTable.AddCell(name)
        Dim imageByte As Byte() = CType(row.Cells(2).Value, Byte())
        Dim myImage As iTextSharp.text.Image = iTextSharp.text.Image.GetInstance(imageByte)
        pdfTable.AddCell(myImage)
    Next

    Dim folderPath As String = "D:\\"

    If Not Directory.Exists(folderPath) Then
        Directory.CreateDirectory(folderPath)
    End If

    Using stream As FileStream = New FileStream(folderPath & "DataGridViewImageExport.pdf", FileMode.Create)
        Dim pdfDoc As Document = New Document(PageSize.A2, 10.0F, 10.0F, 10.0F, 0.0F)
        PdfWriter.GetInstance(pdfDoc, stream)
        pdfDoc.Open()
        pdfDoc.Add(pdfTable)
        pdfDoc.Close()
        stream.Close()
    End Using
End Sub

Screenshots

Form

PDF