Dynamic decision-making under distributional shifts is of fundamental interest in theory and applications of reinforcement learning: The distribution of the environment in which the data is collected can differ from that of the environment in which the model is deployed. This paper presents two novel model-free algorithms, namely the distributionally robust Q-learning and its variance-reduced counterpart, that can effectively learn a robust policy despite distributional shifts. These algorithms are designed to efficiently approximate the $q$-function of an infinite-horizon $γ$-discounted robust Markov decision process with Kullback-Leibler ambiguity set to an entry-wise $ε$-degree of precision. Further, the variance-reduced distributionally robust Q-learning combines the synchronous Q-learning with variance-reduction techniques to enhance its performance. Consequently, we establish that it attains a minimax sample complexity upper bound of $\tilde O(|\mathbf{S}||\mathbf{A}|(1-γ)^{-4}ε^{-2})$, where $\mathbf{S}$ and $\mathbf{A}$ denote the state and action spaces. This is the first complexity result that is independent of the ambiguity size $δ$, thereby providing new complexity theoretic insights. Additionally, a series of numerical experiments confirm the theoretical findings and the efficiency of the algorithms in handling distributional shifts.