This article aims to test the architectural quality indicators defined for the ARV project assessment framework in a new highly efficient residential building. The main categories of Key Performance Indicators (KPIs) are energy, environment, social, architecture, circularity, and economics. Some of the architectural quality indicators relate to the assessment of the building design concepts (e.g., Aesthetics and Visual Qualities, Flexibility and Adaptability, Sufficiency and Adequacy of Space, and others). The other indicators are intended to evaluate the Indoor Environmental Quality (IEQ) conditions of the building’s occupants. The methodology applied included a design team survey to assess how architectural quality concepts were considered in the design phase of the building. In addition, a monitoring campaign and a post-occupancy evaluation (POE) were performed to determine the occupants’ comfort conditions. It was demonstrated that the architectural quality aspects were considered during the design phase, which contributed to the high architectural performance of the building. In addition, the results of the monitoring campaign have shown that the IEQ indicators of the demonstration project are mostly in the high and medium comfort categories based on the European standard EN16798-1:2019, as expected by the ambitions set during the design phase. The proposed methodology was successfully applied in the real case study and proved to be a useful framework for evaluating the design concepts of the building and the IEQ of the occupants.