Antidepressants targeting the serotonergic system have been shown to modulate biases in emotional processing. The effects of serotonergic modulation on the temporal course of emotional processing (accruing within milliseconds) are unknown. Furthermore, it is unknown how serotonin affects different stages of facial emotional processing. The current study investigated the effects of acute serotonin augmentation on event-related potential (ERP) measures associated with 'structural encoding' (N170) and emotion 'expression decoding' (N250 and a late slow-wave positive potential [LPP]) of happy and sad facial stimuli, relative to neutral facial stimuli. The study was a double-blind, placebo-controlled, cross-over design, in which 14 healthy male participants completed a facial recognition task under two acute treatment conditions: 1) placebo (PLB) and 2) 20 mg citalopram (CIT). ERP recording were conducted while subjects viewed neutral, happy and sad facial stimuli. Findings indicated that under PLB, the N170 was not modulated by valence (happy or sad versus neutral), but the N250 and LPP were enhanced for processing happy (relative to neutral) faces. Citalopram had no effect on the N170, but it enhanced the LPP for processing sad (relative to neutral) faces. These findings suggest that serotonin enhancement has selective and temporal effects on emotional face processing, with evidence for modulating processes associated with 'expression decoding' but not 'structural encoding'. The enhanced cortical response to perception of moderately intense sad facial expressions following citalopram administration may relate to the cognitive processing of the social relevance or significance of such ambiguous stimuli.