The use of structural thermal storage is often suggested as a key technology to improve the penetration of renewable energy sources and mitigate potential production and distribution capacity issues. Therefore, a quantitative assessment of the energy flexibility provided by structural thermal energy storage is a prerequisite to instigate a large scale deployment of thermal mass as active storage technologies in an active demand response (ADR) context. In the first part of the work, a generic, simulation-based and dynamic quantification method is presented for the characterization of the ADR potential, or energy flexibility, of structural thermal energy storage. The quantification method is based on three ADR characteristics - i.e. available storage capacity, storage efficiency and power-shifting capability - which can be used to quantify the ADR potential in both design and operation. In the second part of the work, the methodology is applied to quantify the ADR characteristics for the structural thermal energy storage capacity for the different typologies of the Belgian residential building stock. Thereby an in-depth analysis demonstrates the relation between the building properties and its energy flexibility as well as the dependence of the energy flexibility on the dynamic boundary conditions. (C) 2017 Elsevier Ltd. All rights reserved.