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I'd just go buy two 2GB DDR2 (at appropriate speed) sticks, unless you're planning on going 64bit Vista 32bit can't handle anymore. Also RAM will solve a lot of computer speed issues, which you're probably having even with XP.

The problem with buying a new motherboard is you'll want a new chip set, maybe a new power supply, faster RAM and with these custom cases you get from emachines, Dell, HP modifications can be rather limited.

I'd search through newegg.com or Tigerdirect.com for any deals on RAM and if/when you get ready to build a computer start scouring slickdeals for advice and parts deals, normally they know what they're talking about and most of the better deals get posted there.