It matters to memory stability and clock. If your mobo enables dual channel memory, then having an odd number of RAM is BAD by far. You need to read your mobo's manual and see if this is the case.
Some mobos have issues having 3 sticks of DDR installed (like in the case of the K8T800 and NForce 3 based chipset, they both happen to be able to hold 3 DDR sticks max). There is a fair chance that you will have reduced, if not crippled performance in doing so. If you don't care about performance and care more about capacity, then you still may want to test for stability with Memtest86.
Also, note that double sided memory (those that have memory chips on the front and back) have a greater chance of preventing you from reaching optimal memory speeds (and ultimately performance).
Oh.. and memory placement does matter... especially in mobos/cpu combos that use dual channel memory. You need to look in the manual to see what the ideal placement for the RAM is to achieve the highest performance.
Hope this helps you. You are much better off having 1GB of memory in the form of a pair of 512MB single sided memory sticks than what you currently have.