Evidence that bilingualism protects against age-related neurocognitive decline is mixed. One relatively consistent finding is that bilingual seniors have greater grey matter volume (GMV) in regions implicated in executive control (EC) and language processing. Here, we compare the neuroplastic effects of bilingual experience on the EC network of young and aging populations directly, and for the first time we evaluate the extent to which such effects may predict executive control performance across age. We used GMV as an index of neural reserve and response time (RT) performance on the Flanker task for measuring EC efficiency. In the presence of age-related widespread GM deterioration, bilinguals had greater GMV than monolinguals in key regions of interest across age. Moreover, whereas EC performance in monolingual seniors was strictly related to GMV, this was not observed for bilingual seniors or younger participants in either group. Interactions between expected effects-of-age and language group on the relationships between GMV and RT suggested that bilingualism affords differential benefits across the lifespan. In younger participants, greater GMV offered no behavioral benefit on EC performance, whilst it did for seniors. It thus appears that age-related cognitive decline following GMV loss in the EC network is delayed in bilinguals.