The visual attentional blink can be substantially reduced by delivering a task‐irrelevant sound synchronously with the second visual target (T2), and this effect is further modulated by the semantic congruency between the sound and T2. However, whether the cross‐modal benefit originates from audiovisual interactions or sound‐induced alertness remains controversial, and whether the semantic congruency effect is contingent on audiovisual temporal synchrony needs further investigation. The current study investigated these questions by recording event‐related potentials (ERPs) in a visual attentional blink task wherein a sound could either synchronize with T2, precede T2 by 200 ms, be delayed by 100 ms, or be absent, and could be either semantically congruent or incongruent with T2 when delivered. The behavioral data showed that both the cross‐modal boost of T2 discrimination and the further semantic modulation were the largest when the sound synchronized with T2. In parallel, the ERP data yielded that both the early occipital cross‐modal P195 component (192–228 ms after T2 onset) and late parietal cross‐modal N440 component (424–448 ms) were prominent only when the sound synchronized with T2, with the former being elicited solely when the sound was further semantically congruent whereas the latter occurring only when that sound was incongruent. These findings demonstrate not only that the cross‐modal boost of T2 discrimination during the attentional blink stems from early audiovisual interactions and the semantic congruency effect depends on audiovisual temporal synchrony, but also that the semantic modulation can unfold at the early stage of visual discrimination processing.