The possibility that facial expressions of emotion change the affective valence of faces through associative learning was explored using facial electromyography (EMG). In Experiment 1, EMG activity was registered while the participants (N = 57) viewed sequences of neutral faces (Stimulus 1 or S1) changing to either a happy or an angry expression (Stimulus 2 or S2). As a consequence of learning, participants who showed patterning of facial responses in the presence of angry and happy faces, that is, higher Corrugator Supercilii (CS) activity in the presence of angry faces and higher Zygomaticus Major (ZM) activity in the presence of happy faces, showed also a similar pattern when viewing the corresponding S1 faces. Explicit evaluations made by an independent sample of participants (Experiment 2) showed that evaluation of S1 faces was changed according to the emotional expression with which they had been associated. These results are consistent with an interpretation of rapid facial reactions to faces as affective responses that reflect the valence of the stimulus and that are sensitive to learned changes in the affective meaning of faces.