Biomass burning has an impact on atmospheric composition as well as human health and wellbeing. In South Africa, the biomass burning season extends from July to October and affects the aerosol loading and tropospheric ozone concentrations which in turn impact solar ultraviolet radiation (UVR) levels at the surface. Using ground-based observations of aerosols, tropospheric ozone and solar UVR (as well as modelled solar UVR) we investigated the impact of aerosols and tropospheric ozone on solar UVR in August, September, and October over Pretoria. Aerosol optical depth (AOD) and tropospheric ozone reached a peak between September and October each year. On clear-sky days, the average relative difference between the modelled and observed solar Ultraviolet Index (UVI) levels (a standard indicator of surface UVR) at solar noon was 7%. Using modelled UVR—which included and excluded the effects of aerosols and tropospheric ozone from biomass burning—aerosols had a larger radiative effect compared to tropospheric ozone on UVI levels during the biomass burning season. Excluding only aerosols resulted in a 10% difference between the modelled and observed UVI, while excluding only tropospheric ozone resulted in a difference of −2%. Further understanding of the radiative effect of aerosols and trace gases, particularly in regions that are affected by emissions from biomass burning, is considered important for future research.