Physically-based atmospheric correction of optical Earth Observation satellite data is used to accurately derive surface biogeophysical parameters free from the atmospheric influence. While water vapor or surface pressure can be univocally characterized, the compensation of aerosol radiometric effects relies on assumptions and parametric approximations of their properties. To determine the validity of these assumptions and approximations in the atmospheric correction of ESA’s FLEX/Sentinel-3 tandem mission, a systematic error analysis of simulated FLEX data within the O 2 absorption bands was conducted. This paper presents the impact of key aerosol parameters in atmospherically-corrected FLEX surface reflectance and the subsequent Sun-Induced Fluorescence retrieval (SIF). We observed that: (1) a parametric characterization of aerosol scattering effects increases the accuracy of the atmospheric correction with respect to the commonly implemented discretization of aerosol optical properties by aerosol types and (2) the Ångström exponent and the aerosol vertical distribution have a residual influence in the atmospherically-corrected surface reflectance. In conclusion, a multi-parametric aerosol characterization is sufficient for the atmospheric correction of FLEX data (and SIF retrieval) within the mission requirements in nearly 85% (70%) of the cases with average aerosol load conditions. The future development of the FLEX atmospheric correction algorithm would therefore gain from a multi-parametric aerosol characterization based on the synergy of FLEX and Sentinel-3 data.