Social threat detection is important in everyday life. Studies of cortical activity have shown that event-related potentials (ERPs) of motivated attention are modulated during fear conditioning. The time course of motivated attention in learning and extinction of fear is however still largely unknown. We aimed to study temporal dynamics of learning processes in classical fear conditioning to social cues (neutral faces) by selecting an experimental setup that produces large effects on well-studied ERP components (early posterior negativity, EPN; late positive potential, LPP; stimulus preceding negativity, SPN), and then exploring small consecutive groups of trials. EPN, LPP, and SPN markedly and quickly increased during the acquisition phase in response to the CS+ but not the CS-. These changes were visible even at high temporal resolution and vanished completely during extinction. Moreover, some evidence was found for component differences in extinction learning, with differences between CS+ and CS- extinguishing faster for late as compared to early ERP components. Results demonstrate that fear learning to social cues is a very fast and highly plastic process and conceptually different ERPs of motivated attention are sensitive to these changes at high temporal resolution, pointing to specific neurocognitive and affective processes of social fear learning.