In the last decades, several electrophysiological markers have been investigated to better understand how humans precede a signaled event. Among others, the prestimulus microstates' topography, representing the whole brain activity, has been proposed as a promising index of the anticipatory period in several cognitive tasks. However, to date, a clear relationship between the metrics of the pre-stimulus microstates [i.e., the global explained variance (GEV) and the frequency of occurrence (FOO)] and well-known electroencephalography marker of the anticipation (i.e., the alpha power reduction) has not been investigated. Here, after extracting the microstates during the expectancy of the semantic memory task, we investigate the correlations between the microstate features and the anticipatory alpha (8-12 Hz) power reduction (i.e., the event-related de-synchronization of the alpha rhythms; ERD) that is widely interpreted as a functional correlate of brain activation. We report a positive correlation between the occurrence of the dominant, but not non-dominant, microstate and both the mean amplitude of high-alpha ERD and the magnitude of the alpha ERD peak so that the stronger the decrease (percentage) in the alpha power, the higher the FOO of the dominant microstate. Moreover, we find a positive correlation between the occurrence of the dominant microstate and the latency of the alpha ERD peak, suggesting that subjects with higher FOO present the stronger alpha ERD closely to the target. These correlations are not significant between the GEV and all anticipatory alpha ERD indices. Our results suggest that only the occurrence of the dominant, but not nondominant, microstate should be considered as a useful electrophysiological correlate of the cortical activation.