Please refer this code

Ref:

Auto Generate and display Row Number in ASP.Net GridView using C# and VB.Net

Export GridView to Excel without losing gridlines in Excel file in ASP.Net

HTML

<asp:GridView ID="GridView1" runat="server" AutoGenerateColumns="false">
    <Columns>
        <asp:TemplateField HeaderText="Row Number" ItemStyle-Width="100" Visible="false">
            <ItemTemplate>
                <asp:Label ID="lblRowNumber" Text='<%# Container.DataItemIndex + 1 %>' runat="server" />
            </ItemTemplate>
        </asp:TemplateField>
        <asp:BoundField DataField="Name" HeaderText="Name" ItemStyle-Width="150" />
        <asp:BoundField DataField="Country" HeaderText="Country" ItemStyle-Width="150" />
    </Columns>
</asp:GridView>
<br />
<asp:Button ID="btnExport" runat="server" Text="Export To Excel" OnClick="ExportToExcel" />

Namespaces

using System.Data;
using System.Data.SqlClient;
using System.Configuration;
using System.IO;
using System.Drawing;

C#

protected void Page_Load(object sender, EventArgs e)
{
    if (!this.IsPostBack)
    {
        this.BindGrid();
    }
}

private void BindGrid()
{
    string constr = ConfigurationManager.ConnectionStrings["constr"].ConnectionString;
    using (SqlConnection con = new SqlConnection(constr))
    {
        using (SqlCommand cmd = new SqlCommand("SELECT Name, Country FROM Customers"))
        {
            using (SqlDataAdapter sda = new SqlDataAdapter())
            {
                cmd.Connection = con;
                sda.SelectCommand = cmd;
                using (DataTable dt = new DataTable())
                {
                    sda.Fill(dt);
                    GridView1.DataSource = dt;
                    GridView1.DataBind();

                }
            }
        }
    }
}

protected void ExportToExcel(object sender, EventArgs e)
{
    Response.Clear();
    Response.Buffer = true;
    Response.AddHeader("content-disposition", "attachment;filename=GridViewExport.xls");
    Response.Charset = "";
    Response.ContentType = "application/vnd.ms-excel";
    using (StringWriter sw = new StringWriter())
    {
        HtmlTextWriter hw = new HtmlTextWriter(sw);


        this.BindGrid();
        GridView1.Columns[0].Visible = true;
        GridView1.HeaderRow.BackColor = Color.White;
        foreach (TableCell cell in GridView1.HeaderRow.Cells)
        {
            cell.BackColor = GridView1.HeaderStyle.BackColor;
        }
        foreach (GridViewRow row in GridView1.Rows)
        {
            row.BackColor = Color.White;
            foreach (TableCell cell in row.Cells)
            {
                if (row.RowIndex % 2 == 0)
                {
                    cell.BackColor = GridView1.AlternatingRowStyle.BackColor;
                }
                else
                {
                    cell.BackColor = GridView1.RowStyle.BackColor;
                }
                cell.CssClass = "textmode";
            }
        }

        GridView1.RenderControl(hw);

        //style to format numbers to string
        string style = @"<style> .textmode { } </style>";
        Response.Write(style);
        Response.Output.Write(sw.ToString());
        Response.Flush();
        Response.End();
    }
}

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