Millions of adults worldwide are faced with the task of learning a second language (L2). Understanding the neural mechanisms that support this learning process is an important area of scientific inquiry. However, most previous studies on the neural mechanisms underlying L2 acquisition have focused on characterizing the results of learning, relying upon end-state outcome measures in which learning is assessed after it has occurred, rather than on the learning process itself. In this study, we adopted a novel and more direct approach to investigate neural mechanisms engaged during L2 learning, in which we recorded ERPs from beginning adult learners as they were exposed to an unfamiliar L2 for the first time. Learners' proficiency in the L2 was then assessed behaviorally using a grammaticality judgment task, and ERP data acquired during initial L2 exposure were sorted as a function of performance on this task. High-proficiency learners showed a larger N100 effect to open-class content words compared with closed-class function words, whereas low-proficiency learners did not show a significant N100 difference between open- and closed-class words. In contrast, amplitude of the N400 word category effect correlated with learners' L2 comprehension, rather than predicting syntactic learning. Taken together, these results indicate that learners who spontaneously direct greater attention to open- rather than closed-class words when processing L2 input show better syntactic learning, suggesting a link between selective attention to open-class content words and acquisition of basic morphosyntactic rules. These findings highlight the importance of selective attention mechanisms for L2 acquisition.