The AMD Opteron was the very first x86_64 chip. The Athlon 64 followed shortly thereafter and a little while later, Intel's EM64T 5x1/6xx Prescotts and Nocona Xeons came. Transmeta's latest VLIW chip, the Efficeon, can also do x86_64, but it came out later- in 2005. The Itanium can't natively run i386 code like the x86_64 ones can (there's no compatibility mode in the Itanic.) It's its own architecture (IA64) that's not compatible with any x86 code. It can emulate x86 code in software and in a code-morphing hardware module like Transmeta's chips do from x86 <-> VLIW. However, the Itanic's speed with x86 code makes a Crusoe or Efficeon look FAST, and those chips aren't fast my any means, save for speed per watt.
I believe that the 64-bit chip was the MIPS64, followed by the DEC Alpha, the UltraSparc, the RS64, HP-PA, and IBM's Power line of PPC chips. All those came before the x86_64- it was one of the last chips to become 64 bit.