This is just to expand a little bit on Brendan's answer.
For cubic graphs, there is a construction that gives a large number of uniquely 3-edge colourable graphs: start with $K_4$, and repeatedly insert a vertex of degree 3 into a triangular face. This gives a bunch of uniquely-4-colourable planar triangulations (in fact, it is known that this family contains all the uniquely-4-colourable planar triangulations) so the duals of these graphs form a large class of uniquely 3-edge colourable cubic graphs.
Of course, all of these graphs are planar and so at one stage, some optimist conjectured that this was the entire collection of uniquely 3-edge colourable cubic graphs. The $P(9,2)$ example referred to in Brendan's answer is the smallest non-planar cubic graph that is uniquely 3-edge colourable, though lots more such graphs are known.
Related to all this is the question of when a cubic graph has exactly 3 Hamilton cycles. Certainly any uniquely 3-edge colourable cubic graph has exactly 3 Hamilton cycles, but the converse is not true. Thomason found a family of cubic graphs (more generalised Petersen graphs) with exactly 3 Hamilton cycles that are not uniquely 3-edge colourable. The smallest of Thomason's examples is $P(15,2)$ and I wonder if this is actually the smallest possible example. Before you ask, Brendan, I have checked up to 26 vertices, so there might be some examples hiding on 28 vertices but no smaller.