Check this sample code. compare with yours and correct if necessary.My images are stored in img folder of my site My table tblpics contains 2 fields: username and ImageName.  In imagename field image paths are stored as img/id001.jpg. img/id002.jpg and so on..

See my GridView:

<asp:GridView ID="gdvproducts" runat="server" AutoGenerateColumns="False">
        <Columns>
            <asp:BoundField DataField="username" HeaderText="UserName"
                SortExpression="username" />
            <asp:TemplateField HeaderText="Image">
                <ItemTemplate>
                    <asp:Image ID="Image1" runat="server"  ImageUrl='<%# Bind("ImageName") %>'/>
                </ItemTemplate>
            </asp:TemplateField>
        </Columns>
        </asp:GridView>

My Vb.net Code:

Sub fillGV()
        Dim strDatabaseNameAndLocation As String
        strDatabaseNameAndLocation = Server.MapPath("~/App_Data/basic.mdb")
        Dim strSQLCommand As String
        strSQLCommand = "SELECT * FROM tblpics"
        Dim objOleDbConnection As System.Data.OleDb.OleDbConnection
        objOleDbConnection = New System.Data.OleDb.OleDbConnection("Provider=Microsoft.Jet.Oledb.4.0; Data Source=" & strDatabaseNameAndLocation)
        objOleDbConnection.Open()
        Dim objOleDbCommand As System.Data.OleDb.OleDbCommand
        objOleDbCommand = New System.Data.OleDb.OleDbCommand(strSQLCommand, objOleDbConnection)
        Dim objOleDbDataReader As System.Data.OleDb.OleDbDataReader
        objOleDbDataReader = objOleDbCommand.ExecuteReader()
        gdvproducts.DataSource = objOleDbDataReader
        gdvproducts.DataBind()
        objOleDbConnection.Close()
    End Sub

    Protected Sub Page_Load(sender As Object, e As System.EventArgs)
        fillGV()
    End Sub