This study investigated the temporal course of attentional biases for threat-related (angry) and positive (happy) facial expressions. Electrophysiological (event-related potential) and behavioral (reaction time [RT]) data were recorded while participants viewed pairs of faces (e.g., angry face paired with neutral face) shown for 500 ms and followed by a probe. Behavioral results indicated that RTs were faster to probes replacing emotional versus neutral faces, consistent with an attentional bias for emotional information. Electrophysiological results revealed that attentional orienting to threatening faces emerged earlier (early N2pc time window; 180–250 ms) than orienting to positive faces (after 250 ms), and that attention was sustained toward emotional faces during the 250–500-ms time window (late N2pc and SPCN components). These findings are consistent with models of attention and emotion that posit rapid attentional prioritization of threat.