Volatile organic compounds (VOCs) are of first importance in plant defenses since they alter host-plant location by herbivore insects. The worldwide distribution of tomato offers to explore the ecological diversity of defensive VOCs produced by plants supporting a large range of local adaptations. In this study, first, we analyzed the diversity of VOC profiles released by 29 tomato accessions with different natural history and including domesticated and wild relatives. Second, behavioral assays were performed on 10 accessions characterized by strong differences in VOC emissions to elucidate the mechanisms underlying the relationships between the diversity of volatile profiles and antixenosis resistance against a pest of tomato, Tuta absoluta. Among the 77 VOCs detected, a wide diversity of volatile profiles of tomato is reported at both inter- and intra-specific levels. A phylogenetic tree was constructed to study the role of phylogenetic drivers in the distribution of VOC diversity released by tomato. The volatile profile richness and sesquiterpenoid emissions are relatively high in ancestral branches and decreased rapidly with evolution according to an early-burst model. As compared to wild relatives, this study confirmed that domesticated S. lycopersicum with poor volatile profiles and low emissions of sesquiterpenoid is attractive to T. absoluta. Four repellent accessions belonging to S. pennellii, S. habrochaites and S. cheesmaniae were identified. Results stress the importance of both inter- and intra-specific diversity of VOC profiles in antixenosis against T. absoluta. β-myrcene, methyl salicylate and sesquiterpenoids such as (3E,7E)-4,8,12-trimethyltrideca-1,3,7,11-tetraene or α-curcumene could serve as a repellent, whereas δ-elemene and 2-phenylacetaldhyde may help T. absoluta to locate host plants.