In support of cropland monitoring, operational Copernicus Sentinel-2 (S2) data became available globally and can be explored for the retrieval of important crop traits. Based on a hybrid workflow, retrieval models for six essential biochemical and biophysical crop traits were developed for both S2 bottom-of-atmosphere (BOA) L2A and S2 top-of-atmosphere (TOA) L1C data. A variational heteroscedastic Gaussian process regression (VHGPR) algorithm was trained with simulations generated by the combined leaf-canopy reflectance model PROSAILat the BOA scale and further combined with the Second Simulation of a Satellite Signal in the Solar Spectrum (6SV) atmosphere model at the TOA scale. Established VHGPR models were then applied to S2 L1C and L2A reflectance data for mapping: leaf chlorophyll content (Cab), leaf water content (Cw), fractional vegetation coverage (FVC), leaf area index (LAI), and upscaled leaf biochemical compounds, i.e., LAI * Cab (laiCab) and LAI * Cw (laiCw). Estimated variables were validated using in situ reference data collected during the Munich-North-Isar field campaigns within growing seasons of maize and winter wheat in the years 2017 and 2018. For leaf biochemicals, retrieval from BOA reflectance slightly outperformed results from TOA reflectance, e.g., obtaining a root mean squared error (RMSE) of 6.5 μg/cm2 (BOA) vs. 8 μg/cm2 (TOA) in the case of Cab. For the majority of canopy-level variables, instead, estimation accuracy was higher when using TOA reflectance data, e.g., with an RMSE of 139 g/m2 (BOA) vs. 113 g/m2 (TOA) for laiCw. Derived maps were further compared against reference products obtained from the ESA Sentinel Application Platform (SNAP) Biophysical Processor. Altogether, the consistency between L1C and L2A retrievals confirmed that crop traits can potentially be estimated directly from TOA reflectance data. Successful mapping of canopy-level crop traits including information about prediction confidence suggests that the models can be transferred over spatial and temporal scales and, therefore, can contribute to decision-making processes for cropland management.