Prior research has reported vocabulary learning benefits from reading while listening (RWL), but few testable predictions have been made regarding an underlying mechanism for benefits. In this study, reading ahead of the audio was examined as a potential source of benefits during RWL. Fifty-nine participants had their eye movements tracked during a contextualized RWL task embedded with 25 pseudowords 10 times each, followed by three learning outcome measures: form recognition, meaning recognition, and meaning recall. Results indicated that (a) reading ahead facilitated initial form decoding as indexed by gaze durations, especially during early instances; (b) it only predicted the deepest level of vocabulary knowledge tested—meaning recall. These findings indicate that reading ahead may reflect the critical alignment between auditory input, orthographic decoding, and phonological encoding processes during reading, thereby facilitating faster processing when reading ahead than not reading ahead, as well as form-meaning mapping for new words.