This study used a cradle-to-cradle Life Cycle Assessment (LCA) approach to evaluate the environmental potentials of urban pavements. For this purpose, the urban road network of the City of Münster (Germany) was selected as the case study, and comprehensive data for several phases were collected. The entire road network is composed of flexible pavements designed according to specific traffic loads and consists of main roads (MRs), main access roads (MARs), and residential roads (RSDTs). Asphalt materials, pavement structures, and maintenance strategies are predefined for each type of road and are referred to as “traditional” herein. Some pavement structures have two possible maintenance strategies, denoted by “A” and “B”, with distinguished periods of intervention. To evaluate the impact of using recycled materials, we considered alternative pavement structures composed of asphalt materials containing a greater amount of reclaimed asphalt pavement (RAP). The study was carried out considering analysis periods of 20, 50, 80, and 100 years and using two indicators: non-renewable cumulative energy demand (nr-CED) and global warming potential (GWP). The results show that the use of higher amounts of RAP can mitigate negative environmental impacts and that certain structures and maintenance strategies potentially enhance the environmental performance of road pavements. This article suggests initiatives that will facilitate the decision-making process of city administrators to achieve more sustainable road pavement constructions and provides an essential dataset inventory to support future environmental assessment studies, particularly for European cities.