That could be written more succinctly as:

while (defined (my $Line = <TESTFILE>)) {
    next if ($Line =~ m/^#/);
    next if $Line !~ /(option(?:1|2|3|4|6|7))\s*=\s*(.*)/;
    print "$1 = <$2>\n";
}
close (TESTFILE);
[download]

although I doubt very much that the code you have shown so far is your actual code. Maybe if you showed us some real code that you have actually run and that demonstrates the problem you describe.