This research germinates from the statement that cities need to solve the impacts caused by freight transport to improve their sustainability by implementing a set of city logistic measures. Urban freight distribution through environmentally friendly vehicle measures is one of the main sustainable actions being implemented worldwide, with a significant potential to reduce the congestion and pollution levels according to the assessment performed around the world. In this context, this paper aims to explore the use of railways for urban freight transport and then focuses on the potential of shifting from a road to railway system, which uses an advanced demand modelling framework specified and calibrated according to the results of surveys carried out in the study area. Subsequently, the potential benefits of introducing this urban freight transport through the metro system in Rome (Italy) are investigated, showing significant positive effects, both in terms of operational and external costs.