As shown in Scheme 1, the reduction approaches of CO2 have been developed using stable catalysts and renewable reductants (H2) while requiring hazard conditions with corresponding catalyst. Here, recent advancements on catalytic methylations of amines with CO2 in presence of mild hydrides such as hydrosilanes or hydroboranes, which feature CO2 inserted Si-H or B-H bond to form CH3-B or CH3-Si species. In the past decade, tremendous progress was made in the synthesis of formamide by using CO2 as C1 source in the presence of silanes. Meanwhile, related catalytic system can also reduce amides to form amines with hydrosilanes. Therefore, it would be ideal if using CO2 to synthesis the methylated amines can be realized by means of combining these two processes since it is a more economical one-pot process. Actually, recent studies have revealed that reductive methylation of amines only used one bar of CO2. However, the mechanism of the N-methylation of amines with CO2 and hydroboranes is different with hydrosilanes since it is difficult to transform amides to amines by using most hydroboranes, such as BH3NH3 and NaBH4. Taking reductant sodium borohydride (NaBH4) as an example, the N-methylation of amines over all examined CO2 atmosphere can occur only when heated. Herein, we developed a photocatalysis strategy to realize this process at room temperature with a balloon CO2.