The construction of heterojunctions is usually considered as a common strategy to improve charge separation and transfer during the photocatalytic hydrogen evolution reaction (HER) process. Originating from the surficial electrical characteristic of Ti3C2 nanosheets and 2D UiO‐66, a novel 2D/2D Ti3C2/UiO‐66 composite is facilely constructed by the electrostatic self‐assembly process for HER. Higher photocatalytic HER efficiency (265.2 μmol h−1 g−1) is achieved for 2D/2D composites compared to both, pristine 3D UiO‐66 (15.89 μmol h−1 g−1) and 2D UiO‐66 (30.2 μmol h−1 g−1), respectively. The formation of a 2D/2D Ti3C2/UiO‐66 Schottky junction is beneficial for photoinduced electron–hole separation and charge transfer. More exposed active sites stemming from the maintained 2D morphology are simultaneously induced, which is also preferable for HER. Experimental and theoretical analysis reveals the prominent performance attributed to effective charge separation and accelerated electron migration from 2D UiO‐66 to Ti3C2 nanosheets with higher electrochemcial active surface area. Herein, a new route for the construction of efficient photocatalytic systems is provided.

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