Pre-stimulus oscillation activity in the brain continuously fluctuates, but it is correlated with subsequent behavioral and perceptual performance. Here, using fast Fourier transformation of pre-stimulus electroencephalograms, we explored how oscillatory power modulates the subsequent discrimination of perceived simultaneity from non-simultaneity in the audiovisual domain. We found that the over-scalp high beta (20–28Hz), parieto-occipital low beta (14–20Hz), and high gamma oscillations (55–80Hz) were significantly stronger before audition-then-vision sequence when they were judged as simultaneous rather than non-simultaneous. In contrast, a broad range of oscillations, mainly the beta and gamma bands over a great part of the scalp were significantly weaker before vision-then-audition sequences when they were judged as simultaneous versus non-simultaneous. Moreover, for auditory-leading sequence, pre-stimulus beta and gamma oscillatory power successfully predicted subjects' reports of simultaneity on a trial-by-trial basis, with stronger activity resulting in more simultaneous judgments. These results indicate that ongoing fluctuations of beta and gamma oscillations can modulate subsequent perceived audiovisual simultaneity, but with an opposing pattern for auditory- and visual-leading sequences.