Although anecdotally there appear to be differences in the way native speakers use and comprehend their native language, most empirical investigations of language processing study university students and none have studied differences in language proficiency, which may be independent of resource limitations such as working memory span. We examined differences in language proficiency in adult monolingual native speakers of English using an ERP paradigm. ERPs were recorded to insertion phrase structure violations in naturally spoken English sentences. Participants recruited from a wide spectrum of society were given standardized measures of English language proficiency, and two complementary ERP analyses were performed. In between-groups analyses, participants were divided on the basis of standardized proficiency scores into lower proficiency and higher proficiency groups. Compared with lower proficiency participants, higher proficiency participants showed an early anterior negativity that was more focal, both spatially and temporally, and a larger and more widely distributed positivity (P600) to violations. In correlational analyses, we used a wide spectrum of proficiency scores to examine the degree to which individual proficiency scores correlated with individual neural responses to syntactic violations in regions and time windows identified in the between-groups analyses. This approach also used partial correlation analyses to control for possible confounding variables. These analyses provided evidence for the effects of proficiency that converged with the between-groups analyses. These results suggest that adult monolingual native speakers of English who vary in language proficiency differ in the recruitment of syntactic processes that are hypothesized to be at least in part automatic as well as of those thought to be more controlled. These results also suggest that to fully characterize neural organization for language in native speakers it is necessary to include participants of varying proficiency.