Temperature and competition are two of the main factors determining ant community assemblages. Temperature may allow species to forage more or less efficiently throughout the day (in accordance with the maximum activity temperature of each species). Competition can be observed and quantified from species replacements occurring during resource exploitation. We studied the interspecific competitive interactions of ant communities from the Doñana Biological Reserve (southern Spain). Ants were sampled from pitfall traps and baits in three habitats with contrasted vegetation physiognomy (savin forest, pine forest, and dry scrubland). We measured the temperature during the competitive interactions between species and created a thermal competition index (TCI) to assess the relative contribution of temperature and numerical dominance to the competitive outcomes. Temperature had unequal effects on ant activity in each type of habitat, and modulated competitive interactions. The TCI showed that a species' success during pair interactions (replacements at baits) was driven by the proportion of workers between the two competing species and by the species-specific effect of temperature (how advantageous the temperature change is for each species during bait replacement). During competitive interactions, the effect of temperature (higher values of TCI) and numeric supremacy (higher worker proportion) gave higher success probabilities. Interspecific competitive relationships in these Mediterranean ant communities are habitat dependent and greatly influenced by temperature.