Perovskites are prototype electrocatalyts benefiting from their high terrestrial availability and high stability. Electronic state regulation plays a key role in promising higher electrocatalytic efficiencies. Herein, we highlighted a vibronic superexchange in double perovskite to synergistically optimize e(g) electron filling state and increase the formation of active species on the surface of catalysts. Vibronic superexchange of Ni3+-O-Mn3+ in La2NiMnO6 nanoparticles brings the optimal e(g) electron filling state of Mn and Ni ions toward unity. Moreover, a vibronic superexchange interaction of Ni3+-O-Mn3+ induces strong Jahn-Teller distortion of MnO6 and NiO6 octahedra, elongating metal-O bonds, which helps to form the active species of Mn/Ni hydroxide/oxide on the surface of catalysts. Surprisingly, La2NiMnO6 nano particles exhibit superior oxygen evolution reaction (OER) catalytic performance with higher current density and lower Tafel slope than its bulk counterpart. Our finding will be a promising pathway to develop advanced precious-metal-free catalysts.