Agroforestry management has immense potential in enhancing forest carbon sequestration and mitigating climate change. Yet the impact and response mechanism of compound fertilization rates on carbon sinks in agroforestry systems remain ambiguous. This study aims to elucidate the impact of different compound fertilizer rates on soil greenhouse gas (GHG) emissions, vegetation and soil organic carbon (SOC) sinks, and to illustrate the differences in agroforestry systems’ carbon sinks through a one-year positioning test across 12 plots, applying different compound fertilizer application rates (0 (CK), 400 (A1), 800 (A2), and 1600 (A3) kg ha−1). The study demonstrated that, after fertilization, the total GHG emissions of A1 decreased by 4.41%, whereas A2 and A3 increased their total GHG emissions by 17.13% and 72.23%, respectively. The vegetation carbon sequestration of A1, A2, and A3 increased by 18.04%, 26.75%, and 28.65%, respectively, and the soil organic carbon sequestration rose by 32.57%, 42.27% and 43.29%, respectively. To sum up, in contrast with CK, the ecosystem carbon sequestration climbed by 54.41%, 51.67%, and 0.90%, respectively. Our study suggests that rational fertilization can improve the carbon sink of the ecosystem and effectively ameliorate climate change.