Assume that a path must simply connect one edge to another. Then there could be up to 3 separate paths through a hexagon (they do not merge but they may cross).
I have 15 single paths, 33 non-crossing double paths, 15 crossing double paths, 2 non-crossing triples, and 6+6+1 triples with 1,2,3 crossings. The total is 78, but I'm not at all sure this is a good approach or the answer is correct. Perhaps there is a much simpler way to calculate/enumerate.
If rotations and/or reflections are allowed then the number of distinct tiles is much reduced. If paths are allowed to merge when they cross the number is quite a bit higher. Perhaps the question has 3 different answers, but the answer I'm most interested in is the distinct paths on fixed tiles.
[The application is to games like Tantrix, but really a hex maze.]
Edit: there are 30 non-crossing double paths, not 33. The total is 75.
Since the hexagon edges are distinct, the question becomes
Your answer of 78 is wrong and the correct answer is 75; crossings are irrelevant for the answer. The derivation is as follows:
Summing up, we get $15+45+15=75$ arrangements of paths on the fixed hexagon. We can generalise this to other polygons; the number of arrangements $a(n)$ on the fixed $n$-gon is given by A001189, which has $a(6)=75$. Based on how I calculated this specific term above, $a(n)$ has the following formula: $$a(n)=\sum_{k=1}^{\lfloor n/2\rfloor}\frac1{k!}\prod_{j=1}^k\binom n{2j}$$