Mixing state of black carbon (BC) with secondary species has been highlighted as a major uncertainty in assessing its radiative forcing. While recent laboratory simulation has demonstrated that BC could serve as a catalyst to enhance the formation of sulfate, its role in the formation and evolution of secondary aerosols in the real atmosphere remains poorly understood. In the present study, the mixing of BC with sulfate/nitrate in the atmosphere of Guangzhou (China) was directly investigated with a single particle aerosol mass spectrometer (SPAMS). The peak area ratios of sulfate to nitrate (SNRs) for the BC-containing particles are constantly higher than those of the BC-free particles (with negligible BC signals). Furthermore, the seasonal SNR peak is observed in summer and autumn, and the diurnal peak is found in the afternoon, consistent with the trends of radiation-related parameters (i.e., solar radiation and temperature), pointing to the BC-induced photochemical production of sulfate. Such hypothesis is further supported by the multilinear regression and random forest analysis, showing that the variation of SNRs associated with the BC-containing particles could be well explained (R² = ~0.7-0.8) by the radiation-related parameters (> 30% of the variance) and the relative BC content (~20%) in individual particles, but with limited influence of precursors (SO₂/NO_x: < 5%). Differently, the radiation-related factors only explain < 10% of the SNR variation for the BC-free particles. These results provide ambient observational evidence pointing to a unique role of BC on the photochemical formation and evolution of sulfate, which merits further quantitative evaluations.