The present work is aimed at gaining more knowledge on the nature of the relation between land surface temperature (LST) as a biophysical parameter, which is related to the coupled effect of the energy and water cycles, and fire activity over Bulgaria, in the Eastern Mediterranean. In the ecosystems of this area, prolonged droughts and heat waves create preconditions in the land surface state that increase the frequency and intensity of landscape fires. The relationships between the spatial–temporal variability of LST and fire activity modulated by land cover types and Soil Moisture Availability (SMA) are quantified. Long-term (2007–2018) datasets derived from geostationary MSG satellite observations are used: LST retrieved by the LSASAF LST product; fire activity assessed by the LSASAF FRP-Pixel product. All fires in the period of July–September occur in days associated with positive LST anomalies. Exponential regression models fit the link between LST monthly means, LST positive anomalies, LST-T2 (as a first proxy of sensible heat exchange with atmosphere), and FRP fire characteristics (number of detections; released energy FRP, MW) at high correlations. The values of biophysical drivers, at which the maximum FRP (MW) might be expected at the corresponding probability level, are identified. Results suggest that the biophysical index LST is sensitive to the changes in the dynamics of vegetation fire occurrence and severity. Dependences are found for forest, shrubs, and cultivated LCs, which indicate that satellite IR retrievals of radiative temperature is a reliable source of information for vegetation dryness and fire activity.