To achieve a carbon-free economy by 2050, the construction of low-carbon schools in Italy must select the proper structural and technological solutions for the building envelope while ensuring a low economic cost. The aim of this study was to analyze and compare several technological solutions for the building envelope and the related structural solutions in terms of thermo-dynamic properties, energy performance, environmental sustainability parameters, and economic evaluations, to obtain one or more alternatives. After a general study, the binomial load-bearing structure–external wall was investigated given its strong influence on both the environment and the total cost. The solutions were used in a new typological model for the kindergarten. All the solutions are comparable from an energy and environmental point of view, obtaining a primary energy demand of <25 kWh/(m2year) and an environmental impact of <20 kWh/(m2year). However, considering the economic factor and analyzing the binomial load-bearing structure–external wall, the advisable solutions are those that use wooden structures with insulation layer in wood fiber as they have a significantly lower environmental impact, along with the same good energy performance and have an acceptable cost compared to other analyzed solutions.