Repeated exposure to hazards in road construction work zones often generates worker habituation to risks associated with those hazards, a key causal factor in workplace accidents. Understanding the developmental process of risk habituation and providing effective intervention are thus critical to preventing fatalities in road construction work zones. To this end, this study investigates the efficacy of virtual reality (VR) as a behavioral intervention tool to mitigate a decline in vigilant behaviors with habituation to workplace hazards. A VR environment that simulates road construction/maintenance tasks was created and used to repeatedly expose participants to struck-by hazards in road construction operations. An accident was simulated upon the emergence of inattentiveness to hazards within the VR environment. The sustained intervention effect was examined using pretest-posttest analyses to compare the frequency and threshold of participants’ vigilant behaviors. The results revealed that the VR environment elicited a reduction in attentiveness associated with risk habituation over a relatively short period of time, and the simulated accidents in the VR environment generated sustained impacts in the mitigating of the effects of habituation on attention over a week’s time interval. The outcomes of this study contribute to the understanding of how workers’ risk habituation can be measured in a VR environment and provide new knowledge regarding how a VR-based behavioral intervention can mitigate the attentional consequences of habituation to repeatedly exposed workplace hazards.