Road safety funding and management have become important issues in improving the quality of life of road users and there is evidence of a difference in driving behavior and the factor of road use between urban and rural areas, which is, in turn, reflected in different road safety evaluations. The purpose of this study is to assess the financial losses caused by road accidents on Thailand’s highways and the related factors empirically, deploying the willingness-to-pay (WTP) approach. Data were obtained from 640 urban and 960 rural car drivers using a stated choice questionnaire and face-to-face interviews. This study used Correlated Random Parameters Binary Logit with Heterogeneity in Means (CRPBLHM) approach to analyze factors affecting WTP. According to the results, the value of a statistical life and injury for urban drivers was 1.63 times higher than that for rural drivers, and the value of travel time reduction per hour for urban drivers is ∼1.14 times higher than that found for rural drivers. Furthermore, the results of the CRPBLHM model reported that there are significant differences between urban and rural drivers’ safety intentions and WTP. In the urban model, it was found that driving behavior (ticket, seatbelts, and speed) and weekday trips significantly increase the WTP, whereas household size and gender are unobserved characteristics among drivers. The rural model revealed that a driver’s education (bachelor’s and master’s degrees held), and a necessary trip were significantly associated with drivers’ valuation of safety; moreover, it was found that household size, sole earner status, own accident, in possession of a doctoral degree, and being young were significant in acting as unobserved characteristics. The results demonstrated differences in the value of road safety and unobserved heterogeneity among drivers, which influence risk perception and valuation with reference to the area context. Relevant agencies can use the results as a guideline for budget allocation and practical policy-related road safety management.