Javascript, and not just jQuery - though it is the best of the frameworks, it'd be helpful to be familiar with both JS-proper and other frameworks like YUI, prototype, etc.
With JS, you'd have a nice rounded skillset for front-end dev work. You wouldn't be able to function without a team to do the backend - but such is the price that specialists pay.
If, instead, you went the PHP route (and I'll assume you'd also delve into SQL, otherwise it's kind of worthless) - well, you'd be a dime-a-dozen PHP coder that knows HTML and CSS and your lack of experience in both will kill your prospects. There's a lot more to being a backend developer than just PHP and SQL (though some get by amazingly well with nothing more).
Of course, this is all assuming you plan on getting paid for something - if it's just a hobby or scratching an itch, then just do whatever you want. ;)