I had a similar problem when i got a new maxtor drive recently and it reported as PIO mode in windows 2000. It was ATA100 (UDMA mode 5) and my motherboard ide controller supports UDMA66(mode 4). Took me a while to figure it out, but i got it into UDMA like this;
first i got a program called 66to100.exe from maxtor.com, which is basically a dos mode application for switching your hardrive's maximum UDMA mode from 4 to 5, however it also works backwards, allowing you to put the hd into any of the 5 UDMA modes, up or down. You can get this sort of dos mode UDMA mode app for most brands of HD, i had a similar one for my old Seagate drive, just scour the utilities page of your hd makers website for anything metioning UDMA, then read the readme.txt's CAREFULLY.
anyhow, use the .exe from the makers website to regress your hd's max UDMA mode one mode at a time, so you boot to dos, lower the udma, boot into windows and check the ide access mode for udma, then repeat if its still PIO. It took me 3 goes and i ended up with my hardrive in UDMA2 before 2k would use the UDMA. I had enable UDMA66 in the registry and got the ATA100 fix in SP2, but it may be my ide cable. i hope this helps anyhows.