Remote sensing is an established technological solution for bridging critical gaps in volcanic hazard assessment and risk mitigation. The enormous amount of remote sensing data available today at a range of temporal and spatial resolutions can aid emergency management in volcanic crises by detecting and measuring high-temperature thermal anomalies and providing lava flow propagation forecasts. In such thermal estimates, an important role is played by emissivity—the efficiency with which a surface radiates its thermal energy at various wavelengths. Emissivity has a close relationship with land surface temperatures and radiant fluxes, and it impacts directly on the prediction of lava flow behavior, as mass flux estimates depend on measured radiant fluxes. Since emissivity is seldom measured and mostly assumed, we aimed to fill this gap in knowledge by carrying out a multi-stage experiment, combining laboratory-based Fourier transform infrared (FTIR) analyses, remote sensing data, and numerical modeling. We tested the capacity for reproducing emissivity from spaceborne observations using ASTER Global Emissivity Database (GED) while assessing the spatial heterogeneity of emissivity. Our laboratory-satellite emissivity values were used to establish a realistic land surface temperature from a high-resolution spaceborne payload (ETM+) to obtain an instant temperature–radiant flux and eruption rate results for the 2001 Mount Etna (Italy) eruption. Forward-modeling tests conducted on the 2001 ‘aa’ lava flow by means of the MAGFLOW Cellular Automata code produced differences of up to ~600 m in the simulated lava flow ‘distance-to-run’ for a range of emissivity values. Given the density and proximity of urban settlements on and around Mount Etna, these results may have significant implications for civil protection and urban planning applications.