We investigated the neural processes involved in on-line statistical learning and word segmentation. Auditory event-related potentials (ERPs) were recorded while participants were exposed to continuous, nonlinguistic auditory sequences, the elements of which were organized into “tritone words” that were sequenced in random order, with no silent spaces between them. After listening to three 6.6-min sessions of sequences, the participants performed a behavioral choice test, in which they were instructed to indicate the most familiar tone sequence in each test trial by pressing buttons. The participants were divided into three groups (high, middle, and low learners) based on their behavioral performance. The overall mean performance was 74.4%, indicating that the tone sequence was segmented and that the participants learned the tone words statistically. Grand-averaged ERPs showed that word onset (initial tone) elicited the largest N100 and N400 in the early learning session of high learners, but in middle learners, the word-onset effect was elicited in a later session, and there was no effect in low learners. The N400 amplitudes significantly differed between the three learning sessions in the high- and middle-learner groups. The results suggest that the N400 effect indicates not only on-line word segmentation but also the degree of statistical learning. This study provides insight into the neural mechanisms underlying on-line statistical learning processes.