If a motherboard has the "ATX12V" connector (the 4-pin square one with 2 +12 V wires and 2 ground wires), it powers the processor from the 12 V rail. This is also called the "P4" connector because it was introduced with the Pentium 4.
All Socket 423 and 478 boards I've ever seen have had this connector. Ditto Socket T. Many Socket A boards do, but not all. AFAIK all Socket 754, 939, 479, M, S1, AM2, F, J, 603, and 604 boards (IOW, everything since Socket 423 for Intel, and everything after Socket A for AMD) use the 12 V rail. All near-future sockets (AM2+, AM3, etc.) should as well. Some boards have a Molex connector in addition to (or possibly instead of) the ATX12V connector, to provide compatibility with older supplies.
Older ATX boards (Socket 370, Slot A, etc.) should all use the 5 V rail.