Atmospheric aerosols influence the terrestrial carbon cycle through diverse radiative and biogeochemical effects, yet their net impact on vegetation productivity remains contentious and region-specific. To address this, we analyzed the spatiotemporal coupling between aerosol optical depth (AOD) and net primary productivity (NPP) over three African biomes (2013-2023), using multi-source datasets (MODIS, CERES, ERA5, CRU TS). We explicitly distinguished statistically significant relationships (p < 0.05) from non-significant ones when interpreting correlation patterns. Because AOD is an optical measure and does not provide aerosol composition, interpretations involving dust versus smoke are treated as qualitative and indirect. Through structural equation modeling (SEM), we identified two contrasting mechanistic pathways: in the humid Congo Basin rainforest, aerosols were associated with lower NPP via a cooling-mediated pathway (increased cloud albedo leading to reduced temperature and light availability), whereas in the arid savanna, they were associated with more substantial limitations on NPP via a warming-aggravated pathway (increased temperature and potentially coupled water stress). SEM fit was poor for the semi-arid South African plateau, underscoring the dominant role of water availability in strongly water-limited systems. This framework reconciles the paradox of dual aerosol effects by demonstrating that the net impact is dictated by regional climate context. Overall, our conclusions emphasize context-dependent associations rather than direct causal attribution from correlations alone. Our findings provide a process-based understanding that is critical for improving carbon cycle models and for formulating targeted climate adaptation strategies in Africa.