Substantial forestation-induced greening has occurred over South China, affecting the terrestrial carbon storage and atmospheric chemistry. However, these effects have not been systematically quantified due to complex biosphere-atmosphere interactions. Here we integrate satellite observations, forestry statistics, and an improved atmospheric chemistry model to investigate the impacts of forestation on both carbon storage and ozone air quality. We find that forestation alleviates surface ozone via enhanced dry deposition and suppressed turbulence mixing, outweighing the effect of enhanced biogenic emissions. The 2005-2019 greening mitigated the growing season mean surface ozone by 1.4 ± 2.3 ppbv, alleviated vegetation exposure by 15%-41% (depending on ozone metrics) in forests over South China, and increased Chinese forest carbon storage by 1.8 (1.6-2.1) Pg C. Future forestation may enhance carbon storage by 4.3 (3.8-4.8) Pg C and mitigate surface ozone over South China by 1.4 ± 1.2 ppbv in 2050. Air quality management should consider such co-benefits as forestation becomes necessary for carbon neutrality.