Mott-Schottky construction and plasmon excitation represent two highly-efficient and closely-linked coping strategies to the high energy loss of oxygen evolution reaction (OER), but the combined effect has rarely been investigated. Herein, with Ag nanoparticles as electronic structure regulator and plasmon exciter, Ag/CoV-LDH@G nanohybrids (NHs) with Mott-Schottky heterojunction and notable plasmon effect are well-designed. Combining theoretical calculations with experiments, it is found that the Mott-Schottky construction modulates the Fermi level/energy band structure of CoV-LDH, which in turn leads to lowered d-band center (from -0.89 to -0.93), OER energy barrier (from 6.78 to 1.31eV), and preeminent plasmon thermal/electronic effects. The thermal effect can offset the endothermic enthalpy change of OER, promote the deprotonation of *OOH, and accelerate electron transfer kinetics. Whereas the electronic effect can increase the density of charge carriers (from 0.70×1020 to 1.64×1020 cm-3), lower the activation energy of OER (from 30.3 to 17.7kJ mol-1). Benefiting from these favorable factors, the Ag/CoV-LDH@G NHs show remarkable electrocatalytic performances, with an overpotential of 178 and 263mV to afford 10 and 100mA cm-2 for OER, respectively, and a low cell voltage of 1.42V to drive 10mA cm-2 for overall water splitting under near-infrared light irradiation.