I got all my NOS valves before the prices went crazy - got a box full of Mullard/Brimar/Mazda etc... plus some US preamp valves, mostly ECC83/12AX7s but also some ECC81s, ECC82s and a probably around twenty EF86s. then there's the output valves, but thats a smaller collection.
At the minute I'm trying out various oddball valve types that aren't common in amps but are so far turning out to sound great - got an amp wired up for an EF184 which cost £2.00 and sounds every bit as good as an EF86. pinout on the base is different though, so it's a socket rewire job and the preamp will need re-jigged too. however, if you've got the knowhow to do it, you're quids in.
Also got a box of 100 7-pin preamp valves that I'm hopeful will yeild good results - only paid £13.00 for the lot, so it's not exactly a big risk. Got some of the 7-pin preamp valves (6AT6's) in that joblot that Fender used in early tweed amps such as the 5F10 Harvard. Just goes to show, if you look around you can have NOS quality without the price.