Rather than using Convert.ToInt32(string)
you should consider using Int32.TryParse(string, out int)
instead. The TryParse methods are there to help deal with user-provided input in a safer manner. The most likely cause of your error is that the substring you are returning has an invalid string representation of an integer value.
string str = line.Substring(0,1);
int i = -1;
if (Int32.TryParse(str, out i))
{
Console.WriteLine(i);
}