Who was the first to kiss in the Bible?

Answer 1

Probably Adam and Eve.

But if you mean the first recorded one then it is likely to be Jacob when he kissed Isaac at the time when he stole the blessing (which was originally promised to him anyway). This is in Genesis 27: 26-27. This of course was a kiss of respect and endearment, a normal middle eastern custom, although here clouded with deception.

If you mean the first romantic kiss recorded, this could be when Jacob kissed Rachel in Genesis 29:11, although even here this may well have been intentioned in terms of a greeting to a long lost relative as they were related (as recorded in Genesis 29:10-11).