Absorbing aerosols have significant influences on tropospheric photochemistry and regional climate change. Here, the direct radiative effects of absorbing aerosols at the major AERONET sites in East Asia and corresponding impacts on near-surface photochemical processes were quantified by employing a radiation transfer model. The average annual aerosol optical depth (AOD) of sites in China, Korea, and Japan was 1.15, 1.02 and 0.94, respectively, and the corresponding proportion of absorbing aerosol optical depth (AAOD) was 8.61%, 6.69%, and 6.49%, respectively. The influence of absorbing aerosol on ultraviolet (UV) radiation mainly focused on UV-A band (315–400 nm). Under the influence of such radiative effect, the annual mean near-surface J[NO2] (J[O1D]) of sites in China, Korea, and Japan decreased by 16.95% (22.42%), 9.61% (13.55%), and 9.63% (13.79%), respectively. In Beijing–Tianjin–Hebei (BTH) and Yangtze River Delta (YRD) region, the annual average AOD was 1.48 and 1.29, and the AAOD was 0.14 and 0.13, respectively. The UV radiative forcing caused by aerosols dominated by black carbon (BC-dominated aerosols) on the surface was −3.19 and −2.98 W m−2, respectively, accounting for about 40% of the total aerosol radiative forcing, indicating that the reduction efficiency of BC-dominated aerosols on solar radiation was higher than that of other types of aerosols. The annual mean J[NO2] (J[O1D]) decreased by 14.90% (20.53%) and 13.71% (18.20%) due to the BC-dominated aerosols. The daily maximum photolysis rate usually occurred near noon due to the diurnal variation of solar zenith angle and, thus, the daily average photolysis rate decreased by 2–3% higher than that average during 10:00–14:00.