Pre‐stimulus electroencephalogram (EEG) oscillations, especially in the alpha range (8–13 Hz), can affect the sensitivity to temporal lags between modalities in multisensory perception. The effects of alpha power are often explained in terms of alpha's inhibitory functions, whereas effects of alpha frequency have bolstered theories of discrete perceptual cycles, where the length of a cycle, or window of integration, is determined by alpha frequency. Such studies typically employ visual detection paradigms with near‐threshold or even illusory stimuli. It is unclear whether such results generalize to above‐threshold stimuli. Here, we recorded EEG, while measuring temporal discrimination sensitivity in a temporal‐order judgement task using above‐threshold auditory and visual stimuli. We tested whether the power and instantaneous frequency of pre‐stimulus oscillations predict audiovisual temporal discrimination sensitivity on a trial‐by‐trial basis. By applying a jackknife procedure to link single‐trial pre‐stimulus oscillatory power and instantaneous frequency to psychometric measures, we identified a posterior cluster where lower alpha power was associated with higher temporal sensitivity of audiovisual discrimination. No statistically significant relationship between instantaneous alpha frequency and temporal sensitivity was found. These results suggest that temporal sensitivity for above‐threshold multisensory stimuli fluctuates from moment to moment and is indexed by modulations in alpha power. In an audiovisual temporal‐order judgement task, we employed a novel jackknife procedure to quantify temporal sensitivity derived from a psychometric function at the single‐trial level. We found that higher pre‐stimulus alpha power predicted a lower temporal sensitivity, while instantaneous alpha frequency was not predictive of temporal sensitivity. Individual peak‐alpha frequency did not correlate significantly with temporal sensitivity across participants nor did individual peak‐alpha power.