Previous research has indicated that emotional valence can influence the resolution of emotional conflicts, with this effect benefiting from the prioritized processing of negative emotions. In this study, a social learning paradigm was utilized to train participants to associate different neutral faces with distinct social meanings (e.g., stingy, generous). These learned neutral faces were then combined with emotion words of varying valence to create a novel face-word Stroop task. This task was employed to investigate whether social affective associations of different valences continue to impact emotional conflict processing. Concurrently, electroencephalogram data was recorded while participants completed the task. Behavioral results revealed that when participants were presented with neutral faces associated with negative social associations, emotional conflict resolution is facilitated, whereas when faced with neutral faces linked to positive social associations, the emotional conflict effect was significantly present. Consistency between event-related potentials and microstate results indicated that negative social associations facilitated conflict resolution, while positive social associations required participants to recruit more cognitive resources to inhibit irrelevant emotional interference. These findings further expand the factors influencing emotional conflict and relevant neurophysiological explanations.