Presented are the synthesis, characterizations, and reactive surface modification (RSM) of a novel nine atomic layered V4C3T x MXene. With the advantages of the multilayered V4C3T x MXene that can simultaneously support the RSM reaction and keep the inner skeleton stable, a series of amorphous Ni/Fe/V‐ternary oxide hydroxides thin layer can be successfully modified on the surface of the V4C3T x MXene (denoted as MOOH @V4C3T x, M = Ni, Fe, and V) without disrupting its original structure. Attributed to the in situ reconstruction of highly active oxide hydroxide layer, the nanohybrids exhibited an enhanced oxygen evolution reaction (OER) activity and excellent long‐time stability over 70 hours. In particular, a current density of 10 mA cm−2 can be reached by the nanohybrid with the optimized Ni/Fe ratio at an overpotential (η) as low as 275.2 mV, which is comparable to most of the state‐of‐the‐art OER catalysts and better than other MXene‐based derivatives. Demonstrated by the tunable physicochemical properties and excellent structural stability of these nanohybrids, we may envision the promising role of the M4X3‐based MXenes as substrates for a wide range of energy conversion and storage materials. Presented are the novel nine atomic layered V4C3T x MXene and its ternary metal oxide hydroxides modified derivatives (denoted as MOOH@V4C3T x, M = Ni, Fe, and V). The nanohybrids present good OER activity and excellent long‐time stability, which demonstrates the promising future of multilayered M4X3 MXenes as substrates for the reactive synthesis of advanced energy conversion and storage materials.