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Water diffusion in polymers is relevant to a broad range of physicochemical phenomena and technological processes. Although many fields contributed to rapid progress in the fundamental knowledge of water−polymer interactions, detailed understandings come mainly from interpreting numerous experiments. These studies showed that a remarkably rich variety of diffusion forms between water and even seemingly simple polymers. In this review, focusing on the gravimetric and capacitance method, we discuss contradictions and problems existing for water diffusion in polymers in detail from perspectives of experiments and models, focusing on the analysis of error derived from widely used methods, especially for the Brasher−Kingsbury equation. We also provide a perspective on outstanding problems, challenges, and open questions, including water clusters, relaxation, and electrochemical reactions at the metal/polymer interface, as well as expanding the theoretical prospective.