Advanced social behavior, or eusociality, has been evolutionarily profound, allowing colonies of ants, termites, social wasps, and bees to dominate competitively over solitary species throughout the Cenozoic. Advanced sociality requires not just nestmate cooperation and specialization but refined coordination and communication. Here we provide independent evidence that 100-million-year-old Cretaceous ants in amber were social, based on chemosensory adaptations. Previous studies inferred fossil ant sociality from individual ants preserved adjacent to others. We analyzed several fossil ants for their antennal sensilla, using original rotation imaging of amber microinclusions, and found an array of antennal sensilla, specifically for alarm pheromone detection and nestmate recognition, sharing distinctive features with extant ants. Even though Cretaceous ants were stem groups, the fossilized sensilla confirm hypotheses of their complex sociality.