No one has mentioned PerlApp for building executables yet. I have had very good luck with it.
The best thing Perl offers that PHP lacks is a pair of pragmata: strict and warnings. CPAN, the 'Inline' modules, closures, sane sorting functions, POE, and flexible, evolving OOP are neat-o and glorious things, but when I do any PHP hacking I miss strictures most of all.
As others have said, there are a variety of GUI libraries out there. I've used Tk and Wx. Each can be frustrating, and each has it's advantages. Search this site for "which gui" to read lots of discussion on this topic.
Update: I dug a bit and found some more nodes that my search missed:
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