Our daily interactions with the world are shaped by sensory expectations informed by context and prior experiences, which in turn influence how we allocate our attention. Prominent predictive coding models suggest that sensory expectancy and attention interact but disagree on the precise mechanisms. One possibility is that the Ventral Attention Network (VAN), may play a role by facilitating attentional reorienting when expectancy is violated. To test this, we employed an auditory-visual trial-by-trial cueing paradigm in three experiments integrating EEG and fMRI to investigate the role of VAN in violations of cross-modal expectancy. Behavioral results showed faster responses to expected targets, confirming the efficacy of cue-induced expectations in orienting attention to the expected target modality. EEG analyses revealed differences in early (~100 ms latency) event-related potentials (ERPs) to both auditory and visual stimuli when expectations were violated. Unexpected stimuli elicited significantly larger early-latency negative ERPs, across both modalities. Source localization of these ERPs and subsequent fMRI evidence revealed activation in the right VAN. Functional connectivity analyses further showed greater coupling between VAN regions and sensory cortices, with modality-specific pathways involving superior temporal gyrus (STG) for auditory and fusiform gyrus (FG) for visual targets. These findings demonstrate that expectancy violations recruit the VAN to reorient attention and resolve sensory conflict. By coordinating top-down control and bottom-up sensory input, the VAN supports adaptive responses to unexpected stimuli. This work advances our understanding of predictive processing in multisensory perception and highlights the role of VAN in flexible cognitive control.