The aerobic oxidative cleavage of C-C bonds is an attractive and sustainable route for constructing valuable molecules such as esters, nitriles, and amides. Traditionally homogeneous catalytic systems for C-C bond cleavage required harsh conditions, stoichiometric oxidants, and noble metal catalysts to overcome the thermodynamic and kinetic barriers of C-C bonds, imposing environmental concerns of the transformation. Therefore, developing efficient, low-cost, and environmentally benign methods for C-C bond cleavage is of great importance and a cutting-edge area in modern chemistry. This feature article summarizes the sustainable aerobic oxidative C-C bond cleavage method developed by our group in the past 5 years. Fundamental principles in catalyst design, substrate scope, and mechanism for C-C bond cleavage are also discussed.