An assembly sequence is considered to be optimal when is minimizes assembly cost while satisfying assembly constraints. To derive such an optimal sequence for robotic assembly, this paper proposes a method using a simulated annealing algorithm. In this method, an energy funciton is derived inconsideration of both the assembly constraints and the assembly cost. The energy function thus derived is iteratively minimized until no further change in energy occurs. During the minimization, the energy is occationally perturbed probabilistically in order to escape from local minima. The minimized energy yields an optimal assembly sequence. To show the effectiveness of the proposed method, case studies are presented for industrial products such as an electrical relay and an automobil alternator. The performance is analyzed by comparing the results with those of a neural network-based method, based upon the optimal solutions of an expert system.