Higher cardiorespiratory fitness is associated with an increased ability to perform sustained attention tasks and detect rare and unpredictable signals over prolonged periods. The electrocortical dynamics underlying this relationship were mainly investigated after visual stimulus onset in sustained attention tasks. Prestimulus electrocortical activity supporting differences in sustained attention performance according to the level of cardiorespiratory fitness have yet to be examined. Consequently, this study aimed to investigate EEG microstates 2 seconds before the stimulus onset in 65 healthy individuals aged 18–37, differing in cardiorespiratory fitness, while performing a psychomotor vigilance task. The analyses showed that a lower duration of the microstate A and a higher occurrence of the microstate D correlated with higher cardiorespiratory fitness in the prestimulus periods. In addition, increased global field power and occurrence of microstate A were associated with slower response times in the psychomotor vigilance task, while greater global explained variance, coverage, and occurrence of microstate D were linked to faster response times. Our collective findings showed that individuals with higher cardiorespiratory fitness exhibit typical electrocortical dynamics that allow them to allocate their attentional resources more efficiently when engaged in sustained attention tasks.