Due to its cost-effectiveness and repeatability of observations, high resolution optical satellite remote sensing has become a major technology for land use and land cover mapping. However, inventory compilers for the Land Use, Land Use Change, and Forestry (LULUCF) sector are still mostly relying on annual census and periodic surveys for such inventories. This study proposes a new approach based on per-pixel supervised classification using Sentinel-2 imagery from 2016 for mapping greenhouse gas emissions and removals associated with the LULUCF sector in Wallonia, Belgium. The Land Use/Cover Area frame statistical Survey (LUCAS) of 2015 was used as training data and reference data to validate the map produced. Then, we investigated the performance of four widely used classifiers (maximum likelihood, random forest, k-nearest neighbor, and minimum distance) on different training sample sizes. We also studied the use of the rich spectral information of Sentinel-2 data as well as single-date and multitemporal classification. Our study illustrates how open source data can be effectively used for land use and land cover classification. This classification, based on Sentinel-2 and LUCAS, offers new opportunities for LULUCF inventory of greenhouse gas on a European scale.