With the rise in population and urbanization, the demand for affordable housing and other infrastructure is increasing, especially in developing countries. In this context, the incorporation of technology that ensures faster and cheaper construction of structurally sound structures in a safe working condition is gaining relevance. 3D printing is one such technology in which the building material is extruded layer by layer to create the structure of the desired shape. This technique is gaining importance in the construction sector recently due to its advantages in reducing the cost and time of construction. In this background, it is also important to evaluate the long-term sustainability of structures built with 3D printing techniques which in turn is affected by the potential materials that is used to print. Therefore, this study is an attempt to compare two parameters closely related to environmental sustainability, namely thermal comfort and building energy efficiency of residential buildings built with 3D printable concrete, M25 concrete and conventional brick masonry. The results indicate that the performance of 3D printable concrete as the building envelope is lowest in both these criteria, in comparison to other materials. This necessitates further experimental studies in this domain and improvement of materials used for 3D printing in order to address the concerns of sustainability associated with using it in construction. The study, therefore, enlightens on the relevance of examining the sustainability performance of a new technology being implemented in the construction sector to prevent long-term negative environmental impacts.