It depends on several factors:
1.) If your memory is set at 100 instead of 133 in BIOS, it won't make a diference whether you use PC100 or PC133 as either will be operating at 100.
2.) If your CPU is a 100MHz FSB version and your chipset does not support a 100/133 split, your stuck at 100, see #1.
3.) Some motherboard support 100/133 CPU/Memeory bus (Asychronous). If you use PC100 autodetected, your memroy speed will be at the lower 100MHz speed. But you may be able to overclock it to 133 using manual settings
4.) If you are using a board that does NOT support Asychonous memory speed, with a 133FSB processor, you must either overclock the memory or underclock the processor.
5.) If you are using a motherboard that DOES support Asychronous memory speeds with a 133FSB processor, you will either have to run at 133/100 (slower), or manually set your memory to 133/133 (overclocking it).
Overclocking PC100 to 133 does not usually work. Sometimes it does.
Cast not thine pearls before the swine