Look at your logic - you only have the one checkbox. You're unchecking and checking the same control in the employee loop. Does each grid row have a checkbox that should be selected based on the condition the id exists in the employee list?
foreach (GridViewRow row in gv.Rows)
{
Label Id = row.FindControl("lblId") as Label;
var result = Employee.GetEmployeeById(Id.Text);
if (result.Count > 0)
{
CheckBox chkBox = row.FindControl("chkSelected") as CheckBox;
if (chkBox != null)
{
chkBox.Checked = result.Any(x => x.Id.ToString() == Id.Text);
}
}
}