Carbon neutrality has become an urgent mission for the future of mankind. Powering the world with renewable energy from solar CO2 reduction represents a promising way to accomplish this target. Photoelectrochemical (PEC) CO2 reduction, integrating the merits of photocatalysis and electrocatalysis, offers an intriguing and effective approach to realizing solar fuel production and CO2 mitigation in one shot. To stimulate research efforts in PEC CO2 reduction, a comprehensive review of recent advances in this field is presented, with a special emphasis on the general design motives for the assembly of highly efficient PEC cells. First, basic principles and evaluating parameters of PEC CO2 reduction cells are introduced. Then, recent innovative PEC cells with highly active photocathodes for CO2 reduction to different target chemicals are highlighted and the material designing principles are discussed. In addition, the representative self‐biased PEC CO2 reduction cells including the tandem and artificial‐leaf configurations are also addressed. Finally, this review is concluded with remarks on the present achievements in PEC CO2 reduction to different chemicals, pointing out some effective strategies to promote the efficiencies for solar fuel production. A vision of the challenges and opportunities for how to forward PEC CO2 reduction research is further provided.