In Brazil, buses represent the main mode of public transportation. However, in recent years intercity and interstate bus companies have been facing a growing competition with other forms of transportation such as bus companies competitors, illegal transportation companies, chartered buses, and, more recently, air companies. In this scenario characterized by growing competition, it is essential to evaluate the quality of road transportation of passengers. In order to contribute to the analysis of this issue, this paper presents a methodological approach to assess the quality of intercity road transportation of passengers, according to the customers’ perspective. By conducting a case study in a city of almost 500,000 inhabitants from the interior of Rio de Janeiro, an Importance–Satisfaction Analysis (ISA) and an assignment procedure were used in order to obtain: (i) the main factors (criteria) that influence the quality of service intercity road transportation of passengers, (ii) the importance degree of criteria related to road transportation of passengers, (iii) the satisfaction of the users of road transportation under the considered criteria, (iv) the critical criteria/items, and (v) the categories which best represent the quality of service intercity road transportation according to the passengers’ perspective. Finally, several possible corrective actions to improve the quality of services considering each critical item/criterion were highlighted and special recommendations were done for the critical process (ticket sales).