Going off the timelines on Wikipedia, the first version of ASCII was published (1963) before the 0-9,A-F hex notation became widely used (>=1966):
- https://en.wikipedia.org/wiki/ASCII#History
- https://en.wikipedia.org/wiki/Hexadecimal#Cultural_history
The alphanumeric codepoints are well placed hexadecimally-speaking though. I don't imagine that was just an accident. For example, they could've put '0' at 050/0x28, but they put it at 060/0x30. That seems to me that they did have hexadecimal in consideration.