To improve air quality in urban centers, vehicle Inspection and Maintenance (I/M) programs were created to identify highly polluting vehicles and force them to undergo mechanical maintenance. In this context, a methodology, based on a single measurement campaign using a Remote Sensing Device (RSD), is presented in this work to assess the reduction in vehicles emissions obtained from implementing I/M programs. As a case study, an RSD campaign was carried out in Mexico, specifically in Monterrey’s Metropolitan Area (MMA). Approximately 0.4% of the vehicles registered in this region were sampled under similar conditions to those found in I/M programs. The results obtained suggested that 39% of the vehicles would not comply with the current national regulations for circulating vehicles. Following a conservative scenario, the implementation of a vehicle I/M program in this urban center has the potential of reducing the current mass emissions of HC, CO and NO in approximately 69%, 42% and 28%, respectively.