<p>Several toll roads in developing countries have suffered from financial challenges owing to insufficient use. This is partly explained by the absence of empirical evidence on the effects of the perceived factors behind toll road use, particularly in the Global South. This study investigates the role of perceived road service quality and travel characteristics in attracting users to toll roads in Hanoi, Vietnam, where toll roads were introduced alongside existing non-toll networks. A bivariate binary probit model was employed to analyze an individual’s intention to use toll and non-toll roads, with perceived service quality covering accessibility, amenity, safety, quality and comfort, connection level, and serviceability. Data were obtained from paper-based interviews in Hanoi, Vietnam, in 2021, with 304 responses from local travelers. The findings indicated that although toll roads had a higher perceived service quality than non-toll roads, several users had not chosen toll roads, despite being in operation for a decade. This indicates that perceived service quality alone cannot increase toll road use in our case. Policymakers should focus on improving traffic safety and understanding user travel characteristics such as travel frequency, expense opinions, driver status, the importance of roads in daily life, traveler age, toll rate perceptions, and app usage to attract more users to toll roads. This study’s findings suggest that a comprehensive approach is required to enhance toll road use in developing countries.</p>