In comparison to neutral faces, facial expressions of emotion are known to gain attentional prioritization, mainly demonstrated by means of event-related potentials (ERPs). Recent evidence indicated that such a preferential processing can also be elicited by neutral faces when associated with increased motivational salience via reward. It remains, however, an open question whether impacts of inherent emotional salience and associated motivational salience might be integrated. To this aim, expressions and monetary outcomes were orthogonally combined. Participants (N = 42) learned to explicitly categorize happy and neutral faces as either reward- or zero-outcome-related via an associative learning paradigm. ERP components (P1, N170, EPN, and LPC) were measured throughout the experiment, and separately analyzed before (learning phase) and after (consolidation phase) reaching a pre-defined learning criterion. Happy facial expressions boosted early processing stages, as reflected in enhanced amplitudes of the N170 and EPN, both during learning and consolidation. In contrast, effects of monetary reward became evident only after successful learning and in form of enlarged amplitudes of the LPC, a component linked to higher-order evaluations. Interactions between expressions and associated outcome were absent in all ERP components of interest. The present study provides novel evidence that acquired salience impacts stimulus processing but independent of the effects driven by happy facial expressions.