Background: In this study, we explored the interplay between exogenous orienting attention and emotional audiovisual integration (AVI) via electroencephalography (EEG). Methods: We designed a 2 (cue validity: valid, invalid) × 3 (emotion types: happiness, neutral and sadness) × 3 (modality: visual, auditory, audiovisual) discrimination task on the basis of the cue–target paradigm. Twenty-two participants (average age: 21.71 ± 1.84 years; 13 females, 9 males) were enrolled in this experiment. Participants were asked to respond to three emotional stimuli presented in different modalities by pressing a corresponding key. Results: The results indicated faster responses to multisensory stimuli than to unisensory stimuli and to the valid cue condition than to the invalid cue condition, which indicated multisensory advantage and cueing effect occurred. In addition, happiness stimuli induced the fastest response compared with neutral and sadness emotion stimuli. EEG findings indicated a reduction in audiovisual integration induced by valid exogenous orienting in the frontal, central and parietal lobe regions. Moreover, neutral emotional stimuli elicited greater audiovisual integration than stimuli expressing happiness and sadness did. Conclusions: Overall, valid exogenous cues and emotional processing decreased audiovisual integration. The present study sheds light on how exogenous attention modulates emotional audiovisual integration and highlights the complex interactions among attention, sensory processing, and the emotional context in multisensory perception.