Recently, atomically precise metal nanoclusters (NCs) have been widely applied in CO2 reduction reaction (CO2RR), achieving exciting activity and selectivity and revealing structure‐performance correlation. However, at present, the efficiency of CO2RR is still unsatisfactory and cannot meet the requirements of practical applications. One of the main reasons is the difficulty in CO2 activation due to the chemical inertness of CO2. Constructing symmetry‐breaking active sites is regarded as an effective strategy to promote CO2 activation by modulating electronic and geometric structure of CO2 molecule. In addition, in the subsequent CO2RR process, asymmetric charge distributed sites can break the charge balance in adjacent adsorbed C1 intermediates and suppress electrostatic repulsion between dipoles, benefiting for C‐C coupling to generate C2+ products. Although compared to single atoms, metal nanoparticles, and inorganic materials the research on the construction of asymmetric catalytic sites in metal NCs is in a newly‐developing stage, the precision, adjustability and diversity of metal NCs structure provide many possibilities to build asymmetric sites. This review summarizes several strategies of construction asymmetric charge distribution in metal NCs for boosting CO2RR, concludes the mechanism investigation paradigm of NCs‐based catalysts, and proposes the challenges and opportunities of NCs catalysis.