Dynamic decision making under distributional shifts is of fundamental interest in theory and applications of reinforcement learning: The distribution of the environment on which the data is collected can differ from that of the environment on 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 $\gamma$-discounted robust Markov decision process with Kullback-Leibler uncertainty set to an entry-wise $\epsilon$-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 minmax sample complexity upper bound of $\tilde O(|S||A|(1-\gamma)^{-4}\epsilon^{-2})$, where $S$ and $A$ denote the state and action spaces. This is the first complexity result that is independent of the uncertainty size $\delta$, 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.