Enhancing energy efficiency in buildings plays a pivotal role in realizing the ambitious objective of achieving carbon neutrality by 2050, as outlined in the European Green Deal. Roofs represent the technical element most affected by energy phenomena related to heat transfer: in winter, roofing can lose up to 35% of heat, and the summer heat flux can even be higher. This paper provides a catalogue of optimized and sustainable solutions, with a specific focus on standardization and prefabrication principles, for enhancing the energy efficiency of the most prevalent types of roofs that characterize the national residential building heritage. The methodological approach that guided the research presented in this article was based on the identification and study of the most common roofings in the diverse national residential building heritage, followed by their classification according to their construction era. In the context of essential energy retrofitting of deteriorated residential building stock, 21 optimized standardized solutions have been identified. The outcome of performance evaluations of the proposed solutions allowed the implementation of a matrix that can be a valuable support for designers in selecting the most efficient precalculated and prefabricated solutions for the national residential building heritage based on energy performance and sustainability criteria.