The obscured pedestrian-motor vehicle crash has become a serious danger to driving safety. The present study aims to investigate the contingent negative variation (CNV) during the anticipation of an obscured pedestrian-motor vehicle crash in simulated driving. We adopted two cueing tasks: (i) a traditional cognitive paradigm of cueing task that has been widely used to study anticipatory process, and (ii) a modified cueing task in simulated driving scenes, in which Electroencephalogram (EEG) signals of 32 participants were recorded to detect the CNV. Simulated car following and pedestrian crossing tasks were designed to measure anticipation-related driving behaviors. The results showed that both early and late CNVs were observed in two cueing tasks. The mean amplitude of the late CNV during a modified cueing task in simulated driving was significantly larger than that in a traditional cueing task, which was not the case for the early CNV potentials. In addition, both early and late CNVs elicited in simulated driving were significantly correlated with anticipatory driving behaviors (e.g., the minimum time to collision). These findings show that CNV potentials during the anticipation of an obscured pedestrian-motor vehicle crash might predict anticipation-related risky driving behaviors.