Age of first exposure (AoFE) is an important factor that influences the quality of L2 acquisition. This study aims to investigate the AoFE effect on the contextual learning of L2 novel words at the neural level, as measured by the N400 component from event-related potentials (ERPs). Eighty-eight participants were recruited for the experiment of L2 pseudoword learning, which includes a learning session and a testing session. The participants’ EEG data were recorded from the testing session, and the N400 effect was derived from target words that were either congruous or incongruous with the context. The linear mixed model and multiple regression model revealed a positive AoFE effect on the N400 effect in discourses that were designed for testing retrieval of episodic and semantic memory even after accounting for the variance contributed by several confounding factors. In addition to AoFE, the effects of total L2 exposure, L2 proficiency and personality on the L2 novel word learning performance indicated by the N400 effect were also confirmed in the statistical results.