Hexadecimal is base 16. Where decimal uses ten digits (0-9) and rolls over to a new place at ten, hex uses sixteen — 0 through 9, then A, B, C, D, E and F standing in for ten through fifteen. Roll over happens at sixteen, so decimal 16 is written 10 in hex, and decimal 255 is FF.
The reason hex exists has nothing to do with humans finding it natural and everything to do with binary. Sixteen is two to the fourth power, which means one hex digit maps to exactly four binary digits — a nibble — with no remainder and no arithmetic. F is 1111, 8 is 1000, A is 1010, every time, in every context. That clean four-to-one mapping is why a 32-bit value that would take thirty-two ones and zeros collapses into eight readable hex digits, and why you can convert between hex and binary by substitution rather than by calculation.
Decimal has no such relationship with binary. Ten is not a power of two, so converting decimal to binary means actual division, and long binary strings have no tidy decimal shorthand. Hex is the compromise the computing world settled on: compact enough to read aloud, structured enough to translate to machine representation on sight.