An exception of type 'System.Data.SqlClient.SqlException' occurred in System.Data.dll

There are some problems with your code. First I advise to use parametrized queries so you avoid SQL Injection attacks and also parameter types are discovered by framework:

var cmd = new SqlCommand("SELECT EmpName FROM Employee WHERE EmpID = @id", con);
cmd.Parameters.AddWithValue("@id", id.Text);

Second, as you are interested only in one value getting returned from the query, it is better to use ExecuteScalar:

var name = cmd.ExecuteScalar();

if (name != null)
{
   position = name.ToString();
   Response.Write("User Registration successful");
}
else
{
    Console.WriteLine("No Employee found.");
}

The last thing is to wrap SqlConnection and SqlCommand into using so any resources used by those will be disposed of:

string position;

using (SqlConnection con = new SqlConnection("server=free-pc\\FATMAH; Integrated Security=True; database=Workflow; "))
{
  con.Open();

  using (var cmd = new SqlCommand("SELECT EmpName FROM Employee WHERE EmpID = @id", con))
  {
    cmd.Parameters.AddWithValue("@id", id.Text);
  
    var name = cmd.ExecuteScalar();
  
    if (name != null)
    {
       position = name.ToString();
       Response.Write("User Registration successful");
    }
    else
    {
        Console.WriteLine("No Employee found.");
    }
  }
}

I think your EmpID column is string and you forget to use ' ' in your value.

Because when you write EmpID=" + id.Text, your command looks like EmpID = 12345 instead of EmpID = '12345'

Change your SqlCommand to

SqlCommand cmd = new SqlCommand("SELECT EmpName FROM Employee WHERE EmpID='" + id.Text +"'", con);

Or as a better way you can (and should) always use parameterized queries. This kind of string concatenations are open for SQL Injection attacks.

SqlCommand cmd = new SqlCommand("SELECT EmpName FROM Employee WHERE EmpID = @id", con);
cmd.Parameters.AddWithValue("@id", id.Text);

I think your EmpID column keeps your employee id's, so it's type should some numerical type instead of character.

Try this

SqlCommand cmd = new SqlCommand("SELECT EmpName FROM Employee WHERE EmpID=@id", con);
cmd.Parameters.AddWithValue("id", id.Text);