Precise quantification of forest fire impacts is critical for management strategies in support of post-fire mitigation. In this regard, optical remote sensing imagery in combination with spectral unmixing has been widely used to measure fire severity by means of fractional cover of photosynthetic vegetation (PV), non-photosynthetic vegetation (NPV), charcoal (CH) and further ground components such as ash, bare soil and rocks. However, most unmixing analyses have made use of a single post-fire image without accounting for the pre-fire state. We aim to assess fire severity from Sentinel-2 data using a bi-temporal spectral unmixing analysis that provides a quantitative fire impact description and is oriented towards the process of change by including pre-fire and post-fire information. Unmixing was based on Random Forest Regression (RFR) modeling using synthetic training data from a bi-temporal spectral library. We describe fire severity as changes associated with the combustion of photosynthetic vegetation (PV–CH fraction) and dieback of photosynthetic vegetation (PV-NPV fraction). Unburned forest was mapped as stable photosynthetic vegetation (PV-PV fraction). We evaluated our approach on a forest fire that burned in a temperate forest region in eastern Germany in 2018. Independent validation was carried out based on reference fractions obtained from very high-resolution (VHR) imagery such as Plante Scope, SPOT6, orthophotos, aerial photos, and Google Earth. The results underline the effectiveness of our unmixing approach, with Root Mean Squared Errors (RMSE) of 0.072 for PV-CH, 0.09 for PV-NPV, and 0.08 for PV-PV fractions. Most of the errors were caused by spectral similarity between charcoal and shadow effects caused by trees, and the coloring of foliage and NPV in the late phenological season of the post-fire Sentinel-2 image. Based on the two-dimensional feature space of PV-CH and PV-NPV fractions, we calculated two metrics to characterize fire impacts: distance, an indicator of disturbance severity (sum of combustion and dieback), and angle, a measure of disturbance composition (gradient between combustion and dieback). Furthermore, we compared the fraction-based metrics with the difference Normalized Burn Ratio (dNBR). Since the dNBR is most sensitive to combustion and presence of charcoal, it does not fully characterize fire-related vegetation loss associated with dieback. The bi-temporal fraction-based indices provide more ecologically meaningful information on fire severity, particularly for regions that are less prone to severe wildfires such as Central Europe.