Research and development of high thermal insulation materials for the construction sector requires an accurate characterization of the wall's performance, since that is the main causes of thermal exchanges between the internal and external boundaries. This paper presents a test procedure developed within the EU Project EFFESUS for evaluating the steady-state thermal performance of a masonry wall. A large-scale mock-up of the inhomogeneous wall was tested in a guarded hot box (GHB) apparatus before and after the application of an aerogel-based material. The methodology proposed in this paper is structured in the following steps: (i) definition of the wall geometry and the percentage of stone and mortar, using walls' photographic records and geometrical surveys; (ii) precise thermal characterization of the material used; (iii) hygrothermal assessment procedure based on infrared technology (IRT) survey, gravimetric test, and monitoring of the internal relative humidity (RH); (iv) steady-state and dynamic thermal simulation; and (v) detailed set-up of the test using the data retrieved from the thermal surveys and simulations. According to the results of IRT surveys and the dynamic simulations, the mock-up was divided into thermal homogeneous parts, verifying the uniformity of the surface temperature and the heat flux in an isothermal area. This approach was validated both for low and high energy performance walls. Results show that the thermal flux was reduced to one third after the application of the aerogel. (C) 2018 Elsevier B.V. All rights reserved.