This research work synthetizes the energy, economic, and environmental aspects of a novel configurational analysis of four polygeneration schemes designed to fulfill the demands of a multi-family building that includes 12 dwellings. The design aims to meet the requirements (water, electricity, heat and cold air) from Renewable Energy Sources (RESs), in particular by selecting photovoltaic and photovoltaic-thermal panels, thermoelectric generators, and biomass as auxiliaries. Electricity is available from the grid, and no electrical storage is planned. Water and cooling may be produced by alternative technologies that configure the polygeneration alternatives. The case study is in Valencia, a coastal Mediterranean city in Spain. The Design Builder Clima estimated demand calculations, and the system performance was modeled in TRNSYS. Desalination was linked by using EES models. Results show that the suggested schemes offer substantial energy and CO2 savings. The innovative life-cycle analysis applied further enhances the cumulative CO2 savings across the four configurations if the impact of the installations is compared with the conventional external supply. The electric option (combining heat pump and reverse osmosis for cooling and desalination) emerged as the most appealing solution due to its reliability, lower investment cost, and environmental impact.