The present study aimed at investigating whether associated motivational salience causes preferential processing of inherently neutral faces similar to emotional expressions by means of event-related brain potentials (ERPs) and changes of the pupil size. To this aim, neutral faces were implicitly associated with monetary outcome, while participants (N = 44) performed a face-matching task with masked primes that ensured performance around chance level and thus an equal proportion of gain, loss, and zero outcomes. During learning, motivational context strongly impacted the processing of the fixation, prime and mask stimuli prior to the target face, indicated by enhanced amplitudes of subsequent ERP components and increased pupil size. In a separate test session, previously associated faces as well as novel faces with emotional expressions were presented within the same task but without motivational context and performance feedback. Most importantly, previously gain-associated faces amplified the LPC, although the individually contingent face-outcome assignments were not made explicit during the learning session. Emotional expressions impacted the N170 and EPN components. Modulations of the pupil size were absent in both motivationally-associated and emotional conditions. Our findings demonstrate that neural representations of neutral stimuli can acquire increased salience via implicit learning, with an advantage for gain over loss associations.