There's a great article on
Real World Tech about how overclocking actually works.
The short version is, CMOS devices (in this case the transistors and circuits that make up your CPU) operate at different speeds under these conditions:
1) The lower the temperature, the faster they run
2) The higher the voltage, the faster they run
In overclocking, we principally work with #2, as we can't effect a large enough change in #1 to make a difference. The big heatsinks and stuff that we slap on are more designed to reduce the additional heat that higher clock speeds produce to the original spec levels, not reduce it below them.
For an example of overclocking by #1, take a look at the cyrotech systems, which use refriguration to cool the CPU to around -32 (I believe), thus allowing the CPU to run much faster.