The Cray-1 (1976) was probably the first 64-bit CPU.

https://en.wikipedia.org/wiki/64-bit_computing#64-bit_data_t... names Stretch from 01961 as the first natively 64-bit CPU, but maybe there are some that are even older?

I forgot about the IBM 7030 Stretch (1961), which was also 64 bits. The NORC (Naval Ordnance Research Calculator) (1954) had 16 decimal digits, which is sort of 64 bits.