To enhance the interfacial interaction between Si3N4 and epoxy resin/polyacrylate interpenetrating polymer network (IPN) and exert the synergistic effect between Si3N4 and MoS2, Si3N4@MoS2 core–shell hybrid particles (CSs) were successfully prepared by simple hydrothermal method. The as-prepared CSs can significantly enhance the tribological and anti-corrosion properties of epoxy resin/polyacrylate IPN organic matrix. Compared with pure epoxy resin/polyacrylate IPN organic matrix, the composite coating with the optimal amount of 1.5 wt% CSs displays lower friction coefficient and wear rate (reduced by 82% and 83%, respectively), and its impedance modulus at low frequency is increased by 3 orders of magnitude. The enhancement of CSs is mainly attributed to the synergy between Si3N4 with high hardness and MoS2 with self-lubrication and shielding effect of MoS2. Furthermore, Si3N4@MoS2 core–shell structure with synergistic performance characteristics can also effectively enhance the tribocorrosion resistance of epoxy resin/polyacrylate IPN organic matrix. CSs are regarded as promising additive toward wear resistance and corrosion protection.