The exact neural processes behind humans' drive to acquire a new language--first as infants and later as second-language learners--are yet to be established. Recent theoretical models have proposed that during human evolution, emerging language-learning mechanisms might have been glued to phylogenetically older subcortical reward systems, reinforcing human motivation to learn a new language. Supporting this hypothesis, our results showed that adult participants exhibited robust fMRI activation in the ventral striatum (VS)--a core region of reward processing--when successfully learning the meaning of new words. This activation was similar to the VS recruitment elicited using an independent reward task. Moreover, the VS showed enhanced functional and structural connectivity with neocortical language areas during successful word learning. Together, our results provide evidence for the neural substrate of reward and motivation during word learning. We suggest that this strong functional and anatomical coupling between neocortical language regions and the subcortical reward system provided a crucial advantage in humans that eventually enabled our lineage to successfully acquire linguistic skills.