The benefit of the application of geopolymers in the building sector is nowadays undisputed. In addition to good structural characteristics, these are characterized by interesting thermophysical properties, obtained through a production process, that reduces CO2 emissions and could incorporate recycled material, thus responding to environmental sustainability. However, it is noted the lack of studies regarding the in-field thermal performance. Thus, the aim of the present study is to investigate the thermal performance, under real conditions, of an innovative geopolymer-based insulated wall. It incorporates over 70% of net weight of Construction and Demolition Waste materials. The wall is conceived within the European project called “Green INSTRUCT” aimed to realize modular prefabricated building elements, for retrofitting and new construction of buildings. Two wall prototypes are analysed, which differ for the type of lightweight aggregate of geopolymer matrix, 3% by weight: expanded polystyrene or extruded polystyrene. The study refers to almost one year of continuous monitoring within a full-scale test room located in southern Italy. The method developed consists of 5 different phases and it involves also a normative-insulated reference wall. The results show higher insulation level of the proposed wall package, with a reduction of the heat flux of about 66% and more stable indoor thermal conditions, compared to the reference wall. Also the inertial properties are satisfactory, showing an experimental decrement factor equal to 0.05 and a time-shift of decrement factor higher than 6 h. All told, the experimental results can provide valuable insights into the real impact of innovative technology on energy efficiency and indoor thermal comfort.