The only times I can recall are to Eve as a snake, and to Jesus in the desert. Other than that, does he explicitly appear to anyone else?
You ought to ask this to r/christianity or r/catholicism, since this is a theological question and not historical.
You can use a concordance to search for "devil" and "Satan" to find examples such as Luke 22 1-6, Jude 1:9. Not to mention Revelation.