Evaluating multisensory emotional content is a part of normal day-to-day interactions. We used fMRI to examine brain areas sensitive to congruence of audiovisual valence and their overlap with areas sensitive to valence. Twenty-one participants watched audiovisual clips with either congruent or incongruent valence across visual and auditory modalities. We showed that affective congruence versus incongruence across visual and auditory modalities is identifiable on a trial-by-trial basis across participants. Representations of affective congruence were widely distributed with some overlap with the areas sensitive to valence. Regions of overlap included bilateral superior temporal cortex and right pregenual anterior cingulate. The overlap between the regions identified here and in the emotion congruence literature lends support to the idea that valence may be a key determinant of affective congruence processing across a variety of discrete emotions.