Learning a new word requires discrimination between a novel sequence of sounds and similar known words. We investigated whether semantic information facilitates the acquisition of new phonological representations in adults and whether this learning enhancement is modulated by overnight consolidation. Participants learned novel spoken words either consistently associated with a visual referent or with no consistent meaning. An auditory oddball task tested discrimination of these newly learned phonological forms from known words. The MMN, an electrophysiological measure of auditory discrimination, was only elicited for words learned with a consistent semantic association. Immediately after training, this semantic benefit on auditory discrimination was linked to explicit learning of the associations, where participants with greater semantic learning exhibited a larger MMN. However, although the semantic-associated words continued to show greater auditory discrimination than nonassociated words after consolidation, the MMN was no longer related to performance in learning the semantic associations. We suggest that the provision of semantic systematicity directly impacts upon the development of new phonological representations and that a period of offline consolidation may promote the abstraction of these representations.