To get best performance (dual channel vs single channel memory access), you need to match sizes. In real world, however, dual channel access do not necessarily translate into significant performance increase... could be more like 10% or so.
Also, to get dual channel, you need to match a couple of other things and not just their size. RAM speed on both modules must be identical as well as chip configuration (e.g., 8x64 MB dual sided). So if you are ordering iMac from Apple BTO with 1 GB and ordering 2nd 1 GB module elsewhere, you need to be sure that they are the same.