Changes in the snow cover extent are both a cause and a consequence of climate change. Optical remote sensing with heliosynchronous satellites currently provides snow cover data at high spatial resolution with daily revisiting time. However, high latitude image acquisition is limited because reflective sensors of many satellites are switched off at high solar zenith angles (SZA) due to lower signal quality. In this study, the relevance and reliability of high SZA acquisition are objectively quantified in the purpose of high latitude snow cover detection, thanks to the PROBA-V (Project for On-Board Autonomy-Vegetation) satellite. A snow cover extent classification based on Normalized Difference Snow Index (NDSI) and Normalized Difference Vegetation Index (NDVI) has been performed for the northern hemisphere on latitudes between 55°N and 75°N during the 2015–2016 winter season. A stratified probabilistic sampling was used to estimate the classification accuracy. The latter has been evaluated among eight SZA intervals to determine the maximum usable angle. The global overall snow classification accuracy with PROBA-V, 82% ± 4%, was significantly larger than the MODIS (Moderate-resolution Imaging Spectroradiometer) snow cover extent product (75% ± 4%). User and producer accuracy of snow are above standards and overall accuracy is stable until 88.5° SZA. These results demonstrate that optical remote sensing data can still be used with large SZA. Considering the relevance of snow cover mapping for ecology and climatology, the data acquisition at high solar zenith angles should be continued by PROBA-V.