Poor alertness levels and related changes in cognitive efficiency are common when performing monotonous tasks such as extended driving. Recent studies have investigated driver alertness decrement and possible strategies for modulating alertness with the goal of improving reaction times to safety critical events. However, most studies rely on subjective measures in assessing alertness changes, while the use of olfactory stimuli, which are known to be strong modulators of cognitive states, has not been commensurately explored in driving alertness settings. To address this gap, in the present study we investigated the effectiveness of olfactory stimuli in modulating the alertness state of drivers and explored the utility of electroencephalography (EEG) in developing objective brain-based tools for assessing the resulting changes in cortical activity. Olfactory stimulation induced a significant differential effect on braking reaction time. The corresponding effect to the cortical activity was characterized using EEG-derived metrics and the devised machine learning framework yielded a high discriminating accuracy (92.1%). Furthermore, neural activity in the alpha frequency band was found to be significantly associated with the observed drivers’ behavioral changes. Overall, our results demonstrate the potential of olfactory stimuli to modulate the alertness state and the efficiency of EEG in objectively assessing the resulting cognitive changes.