In order to assess sustainability of products and processes, different methodologies have been developed and used in the last years. In the road pavement construction area, most methodologies used for Life Cycle Assessment (LCA) are essentially focused in the construction phase. The present paper analyses the importance of the use phase of a road in the LCA of different paving alternatives, namely by evaluating energy consumption and gaseous emissions throughout the road pavement's life. Therefore, a new LCA methodology for road pavements was developed, and the results of its application to a case study involving the construction of alternative pavement structures are discussed. The study intends to assess the influence of using more sustainable paving construction alternatives (asphalt recycling vs. conventional asphalt mixtures), and/or different surface course materials (which have a higher influence on the rolling resistance and, therefore, affect the performance during the use phase). The LCA results obtained for this case study showed that the reductions in energy consumption and gaseous emissions obtained during the use phase, for pavement alternatives with a lower rolling resistance surface course, are higher than the total amount of energy consumption and gas emissions produced during construction. It is therefore clear that some improvements in the characteristics of the surface course may have an effect over the road use phase that will rapidly balance the initial costs and gas emissions of those interventions. The LCA results obtained also showed that the sustainability of pavement construction may also be improved using recycled asphalt mixtures.