3D concrete printing has gained tremendous popularity as a promising technique with the potential to remarkably push the boundaries of conventional concrete technology. Enormous research efforts have been directed towards improving the material properties and structural safety of 3D printed concrete (3DPC) over the last decade. In contrast, little attention has been accorded to its sustainability performance in the built environment. This study compares the energy efficiency, operational carbon emission, and thermal comfort of air cavity 3DPC building envelopes against insulated models. Four insulations, namely expanded polystyrene (EPS), extruded polystyrene (XPS), polyurethane foam (PUF), and fiberglass (FG), are iteratively paired with three different 3DPC mix designs, and their resulting performances are reported. A numerical optimization analysis is performed to obtain combinations of 3DPC building models and insulation with the least energy expenditure, carbon production, and thermal efficiency. The results indicate that insulation considerably enhances the overall environmental performance of 3DPC structures. The optimization process also demonstrates the potential of using 3D printable fiber reinforced engineered cementitious concrete (3DPFRECC) with polyurethane infill for amplified sustainable performance in modern construction.