Two neurodevelopmental disorders, Williams syndrome (WS) and autism, are both commonly described as having opposite social profiles: social avoidance in autism vs hypersociability in individuals with WS. The goal of this study was to contrast the brain activity associated with language processing in these two populations, in order to understand the very likely interplay between the use of language and the sociability dimension, on which these disorders diverge. Towards this aim, the N400 component of the event-related potentials was used to quantify the processing of semantic integration in these two populations. Results revealed that individuals with WS showed a significantly larger N400 effect, as compared to both typical controls and individuals with autism, while the latter group demonstrated the smallest N400 effect. The findings demonstrate quite opposite profiles of neural correlates of language processing in WS and autism, mirroring their contrasting social phenotypes.