The development of a cost‐competitive and efficient electrocatalyst is both attractive and challenging for hydrogen production by hydrogen evolution reaction (HER). Herein, a facile glycol reduction method to construct Ru nanoclusters coupled with hierarchical exfoliated‐MXene/reduced graphene oxide architectures (Ru‐E‐MXene/rGA) is reported. The hierarchical structure, formed by the self‐assembly of graphene oxides, can effectively prohibit the self‐stacking of MXene nanosheets. Meanwhile, the formation of the MXene/rGA interface can strongly trap the Ru³⁺ ions, resulting in the uniform distribution of Ru nanoclusters within Ru‐E‐MXene/rGA. The boosted catalytic activity and underlying catalytic mechanism during the HER process are proved by density functional theory. Ru‐E‐MXene/rGA exhibits overpotentials of 42 and 62 mV at 10 mA cm⁻² in alkaline and acidic electrolytes, respectively. The small Tafel slope and charge transfer resistance (R_ct) values elucidate its fast dynamic behavior. The cyclic voltammetry (CV) curves and chronoamperometry test confirm the high stability of Ru‐E‐MXene/rGA. These results demonstrate that coupling Ru nanoclusters with the MXene/rGA heterostructure represents an efficient strategy for constructing MXene‐based catalysts with enhanced HER activity.