I was one of those weird users who used the 64-bit version of Windows XP, with what I'm pretty sure was an Athlon 64 X2, both the first 64-bit chip and first dual-core one that I had.
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"The 64-bit versions of Windows NT were originally intended to run on Itanium and DEC Alpha; the latter was used internally at Microsoft during early development of 64-bit Windows. This continued for some time after Microsoft publicly announced that it was cancelling plans to ship 64-bit Windows for Alpha. Because of this, Alpha versions of Windows NT are 32-bit only."