The development of reliable catalysts with both excellent activity and recyclability for carbon dioxide (CO2) hydrogenation is challenging. Herein, a ternary hybrid heterogeneous catalyst, involving mononuclear Ru complex, N, P-containing porous organic polymers (POPs), and mesoporous hollow carbon spheres (Ru3+-POPs@MHCS) is reported for CO2 hydrogenation to formate. Based on comprehensive structural analyses, we demonstrated that Ru3+-POPs were successfully immobilized within MHCS. The optimized Ru3+-0.5POPs@MHCS catalyst, which was obtained with about 5 wt.% Ru3+ and 0.5 mmol POPs polymers confined into 0.3 g MHCS, exhibited high catalytic activity for CO2 hydrogenation to formate (turnover number (TON) > 1,200 for 24 h under mild reaction conditions (4.0 MPa, 120 °C)) and improved durability, compared to Ru3+ catalysts without POPs polymers (Ru3+-MHCS) and unencapsulated MHCS (Ru3+-0.5POPs) catalysts. The improved catalytic performance is attributed to the high surface area and large pore volume of MHCS which favors dispersion and stabilization of Ru3+-POPs. Furthermore, the MHCS and POPs showed high CO2 adsorption ability. Ru3+-POPs encapsulated into MHCS reduces the activation energy barrier for CO2 hydrogenation to formate.