Emotion is an emergent construct of multiple distinct neural processes. EEG is uniquely sensitive to real‐time neural computations, and thus is a promising tool to study the construction of emotion. This series of studies aimed to probe the mechanistic contribution of the late positive potential (LPP) to multimodal emotion perception. Experiment 1 revealed that LPP amplitudes for visual images, sounds, and visual images paired with sounds were larger for negatively rated stimuli than for neutrally rated stimuli. Experiment 2 manipulated this audiovisual enhancement by altering the valence pairings with congruent (e.g., positive audio + positive visual) or conflicting emotional pairs (e.g., positive audio + negative visual). Negative visual stimuli evoked larger early LPP amplitudes than positive visual stimuli, regardless of sound pairing. However, time frequency analyses revealed significant midfrontal theta‐band power differences for conflicting over congruent stimuli pairs, suggesting very early (∼500 ms) realization of thematic fidelity violations. Interestingly, late LPP modulations were reflective of the opposite pattern of congruency, whereby congruent over conflicting pairs had larger LPP amplitudes. Together, these findings suggest that enhanced parietal activity for affective valence is modality independent and sensitive to complex affective processes. Furthermore, these findings suggest that altered neural activities for affective visual stimuli are enhanced by concurrent affective sounds, paving the way toward an understanding of the construction of multimodal affective experience.