Photocatalytic reduction of CO2 to solar fuels and/or fine chemicals is a promising way to increase the energy supply and reduce greenhouse gas emissions. However, the conventional reaction system for CO2 photoreduction with pure H2O or sacrificial agents usually suffers from low catalytic efficiency, poor stability, or cost‐ineffective atom economy. A recent surge of developments, in which photocatalytic CO2 valorization is integrated with selective organic synthesis into one reaction system, indicates an efficient modus operandi that enables sufficient utilization of photogenerated electrons and holes to achieve the goals for sustainable economic and social development. In this Review we discuss current advances in cooperative photoredox reaction systems that integrate CO2 valorization with organics upgrading based on heterogeneous photocatalysis. The applications and virtues of this strategy and the underlying reaction mechanisms are discussed. The ongoing challenges and prospects in this area are critically discussed. The photoredox‐catalyzed win–win coupling strategy, in which CO2 valorization is integrated with organic synthesis in one reaction system, provides a promising approach that enables sufficient utilization of excited electrons and holes to achieve feasible and sustainable light‐mediated artificial photosynthesis.