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Large-scale concrete 3D printing and digital construction has brought enormous potential to expand the design space of building components (e.g., building envelope) for the integration of multiple architectural functionalities including energy saving. In this research, a modular 3D printed vertical concrete green wall system – namely the 3D-VtGW, was developed. The 3D-VtGW envelope was assembled with prefabricated (3D printed) multifunctional wall modular elements, which serves as the enclosure of the building as well as the backbone for a green wall system to improve building’s energy efficiency. Using this design concept and large-scale concrete 3D printing, a prototype commercial building was built in Nanjing, China. To quantify the energy-saving potential of the 3D-VtGW system, a thermal network model was developed to simulate the thermal behavior of buildings with 3D-VtGW system and for thermal comfort analysis. Whole-building energy simulation was carried out using Chinese Standard Weather Data (CSWD) o Nanjing, China. The simulation results indicate that the building with 3D-VtGW exhibited prominent potential for energy saving and improved thermal comfort. The integrated greenery system in 3D-VtGW largely reduces wall exterior surface temperature and through-wall heat flux via the combined effects of plant shading, evapotranspiration, and heat storage from soil. This study presents the immense opportunities brought by digital fabrication and construction to extend the design space and function integration in buildings.