Parts Express (subsidiary of Sonic Frontiers) has a selection of high end cables that you can terminate yourself and save quite a bit. Check it out.
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It's actually http://www.partsconnection.on.ca. Also, there's Jon Risch's DIY cable page at NBCi (search for his name at Yahoo and you'll find a link to it). Wellborne Labs also sells cable parts, though with a smaller selection of bulk cable to choose from. And the Cable forum at audioasylum.com contains a lot of discussion about DIY cables. Have fun!
For silver OR copper wire, Homegrown is a great site. They actually have many more wires than the 2(22 awg teflon insulated silver or copper) they list + silver solder. Just e-mail him, he's very responsive. Also, you can try Pure Silver Sound for silver and components. And a third is Orca Design, for copper and GREAT accesories. They are the parts division of JMLabs. They offer AXON components(wire[PVC or polyethylene - I forget which - insulated 22 awg copper], EXCELLENT connectors of all types, resistors, capacitors, inductors[I am not a fan of their inductors - use North Creek or Alpha Core Goertz instead], etc.), Focal drivers, LOTS of plans, kits, etc. Kimon Bellas is the head of US operations, and if ever there was an unsung hero in this field, it is he. His products and help offer us the best in speaker/wire/components for lower than mid-fi prices.
I hope you won't repeat my mistake and buy wire as thick as 22 gauge, or even 24 2 or 25 gauge, no matter how pure, no matter how cheap. It just won't made a good cable, by today's standards. I have hundreds of feet of high quality, as measured by purity, in basement storage, now that I've finally learned that it's hopeless, good for no audio purpose. The same can be said for even more expensive Kimber AGSS, multistranded silver. I've proved this to myself by direct comparisons. You can homemake a fairly good cable, you can beat AudioQuest Diamond, for example, but why go to all the trouble when your best effort will be so inferior to the least expensive cable of The Company Name I Dare Not Mention (for fear of more insulting posts in this forum)? Try to find wire no thicker than 32 gauge, and use only one strand for signal. Geometry is another issue, but your question was just about materials.
Several of the posts have mentioned "HomeGrownAudio". A friend recently assembled one of the all-silver sets of IC's, and the quality of the wire and jacks is very good. If your objective is primarily to save money, rather than have the DIY experience, you should also check out "www.bettercables.com". I have several sets of their cables and am very impressed with the build quality and price (very reasonable).