Wildfires pose a growing threat to Mediterranean ecosystems. This study employs advanced classification techniques for shrub fractional cover mapping from satellite imagery in a fire-prone landscape in Quinta da França (QF), Portugal. The study area is characterized by fine-grained heterogeneous land cover and a Mediterranean climate. In this type of landscape, shrub encroachment after land abandonment and wildfires constitutes a threat to ecosystem resilience—in particular, by increasing the susceptibility to more frequent and large fires. High-resolution mapping of shrub cover is, therefore, an important contribution to landscape management for fire prevention. Here, a 20 cm resolution land cover map was used to label 10 m Sentinel-2 pixels according to their shrub cover percentage (three categories: 0%, >0%–50%, and >50%) for training and testing. Three distinct algorithms, namely Support Vector Machine (SVM), Artificial Neural Networks (ANNs), and Random Forest (RF), were tested for this purpose. RF excelled, achieving the highest precision (82%–88%), recall (77%–92%), and F1 score (83%–88%) across all categories (test and validation sets) compared to SVM and ANN, demonstrating its superior ability to accurately predict shrub fractional cover. Analysis of confusion matrices revealed RF’s superior ability to accurately predict shrub fractional cover (higher true positives) with fewer misclassifications (lower false positives and false negatives). McNemar’s test indicated statistically significant differences (p value < 0.05) between all models, consolidating RF’s dominance. The development of shrub fractional cover maps and derived map products is anticipated to leverage key information to support landscape management, such as for the assessment of fire hazard and the more effective planning of preventive actions.