The integration of highly accessible electro‐active sites and the high conductivity can enhance the catalytic performance of catalysts. Herein, we report a facile ambient growth of FeOOH nanosheets (NSs) on the surface of Ti3C2 nanosheets to fabricate the hierarchical FeOOH NSs/Ti3C2. The hierarchical structure efficiently suppresses agglomeration of nanosheets to expose maximal electro‐active surface, and provides strong interfacial interaction between FeOOH and Ti3C2 that facilitates fast charge transfer, leading to enhanced electrocatalytic performance. Specifically, the FeOOH NSs/Ti3C2 achieves a current density of 10 mA cm−2 at 1.63 V vs RHE with a Tafel slope of 95 mV dec−1, and possesses excellent OER stability with negligible attenuation of current density after 30 h. This work represents that growth of poor conductive active materials on 2D MXene can boost the catalytic performance of electrocatalyst.