Python was released in 1991 with 1.0 in 1994, PyPI is newer (the date listed there appears to be when it went online.)

https://www.pypa.io/en/latest/history.html#before-2013 says PyPI was launched in 2003.

Wikipedia agrees with the activity history PyPI themselves posted in TFA and indicates the index at its original home under python.org went live in November 2002, and PEP 301 was posted with present-tense descriptions of the URL where the index was available on 11/8/2002. But,

AFAICS PEP 301 linked only to a demo site until April 2003:

https://github.com/python/peps/commit/c773b1b2ce0a2817