As far as using PHP, you should be good to go (if you have 100,000 files to scan this will be expensive with pretty much any scripting language you use. However, if it's Web based PHP is a sure bet!)
As far as MySQL, well, this depends on how much querying you're planning to do. If you're looking for the record that has a file id, we'll say, of "on-top-of-old-smokie.mp3" so you can return some information about it, no problem, 100,000 records shouldn't wipe you out. If you're planning on returning data from 100,000 records with each query to provide data for parsing with PHP, well, I'll just say, try it.
Again, depends on what you wanna do. Just food for thought...when MySQL 4.0 comes out of beta, it will rock! I've seen bench marks where it rivals Oracle easy.