Further to Eric's good advice: Do you already have access to a mips64 version of glibc? (You said in your message that you'd tried a native build, but I wasn't sure whether that was using a 32-bit OS or a 64-bit OS)
It's tricky to build a toolchain and glibc in tandem (i.e. when neither is available beforehand), and like Eric says, crosstool is probably the best thing to use for that. (Although to be honest, I don't use crosstool myself, so I'm not 100% sure whether it supports mips64 or not.) On the other hand, if you already have access to a 64-bit glibc, you should be able to build the toolchain in the same way as any other version of gcc. So if you do have access to a 64-bit glibc: which version(s) of gcc are you trying to build, and what errors do you get? Richard