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Post-fire geomorphic processes and associated risks are an important threat in Mediterranean environments. Currently, post-fire mass movement prediction has limited applications across the Mediterranean despite the abundance of both forest fires and landslide/debris flow disasters. This work applies a debris flow generation likelihood model to evaluate the probability of mass movement phenomena in different catchments of a burnt area, after a catastrophic fire near Schinos (Attica, Greece) in 2021. Then, it uses field observations from the area, recording mass movement phenomena after high-intensity rainfall events, to validate the results. The findings show that the model is successful in determining the probability of debris flow generation in the 21 basins of the study area, ranging from 0.05 to 0.893. The probability values show a statistically significant correlation (sig. = 0.001) with the actual debris flow occurrences in the area, and satisfactory results in terms of the model’s predictive ability, functioning well within the particular geo-environmental characteristics of the Mediterranean environment. The results establish the reliability of the approach as a tool to assess mass movement risks in a region with an abundance of post-fire related hazards and disastrous events.