Abstract: Existing studies on provably efficient algorithms for Markov games (MGs) almost exclusively build on the ``optimism in the face of uncertainty'' (OFU) principle. This work focuses on a distinct approach of posterior sampling, which is celebrated in many bandits and reinforcement learning settings but remains under-explored for MGs. Specifically, for episodic two-player zero-sum MGs, a novel posterior sampling algorithm is developed with \emph{general} function approximation. Theoretical analysis demonstrates that the posterior sampling algorithm admits a $\sqrt{T}$-regret bound for problems with a low multi-agent decoupling coefficient, which is a new complexity measure for MGs, where $T$ denotes the number of episodes. When specializing to linear MGs, the obtained regret bound matches the state-of-the-art results. To the best of our knowledge, this is the first provably efficient posterior sampling algorithm for MGs with frequentist regret guarantees, which extends the toolbox for MGs and promotes the broad applicability of posterior sampling.