As interest in harvesting green energy and utilizing renewable energy in the building sector has increased, the concept of Net Zero Energy Structure (NZES) has been highlighted. In this study, a strategy to develop the sustainable triboelectricity-assisted NZES is proposed. The multi-walled Carbon nanotube (MWCNT)-incorporated Cement Composite (CCC) is adopted as the structural/electrical member of the triboelectric nanogenerator (TENG) and the polyvinylidene difluoride-trifluoroethylene (PVDF-TrFE) nanofiber is directly electrospun onto the surface of CCC to act as the contact layer of the CCC-based TENG. The optimal concentration of incorporated MWCNT, C_MC, is determined to be 1 vol%, considering the compressive strength and electrical property of CCC. The conditions of the electrospinning process for configuring the electrospun PVDF-TrFE nanofibrous mat on the surfaces of CCCs with various shapes are investigated. The electrical output performance of the CCC-TENG is characterized by varying the various environmental and operational parameters. The direct electrospun PVDF-TrFE nanofibrous mat on the CCC-TENG significantly increases the output voltage to approximately 6 times that of flat TENG. The maximum peak power generated from CCC-TENG reaches 60.9 μW when the connected load resistance is 50 MΩ. Furthermore, as a proof-of-concept, the reconstructability of the PVDF-TrFE nanofibrous mat using the direct electrospinning process, as well as the restorations in terms of surface micro/nanostructures and electrical output performance, are demonstrated. Given the wide range of applications of cement and various functionalities of direct electrospinning technology, the sustainable triboelectricity-assisted NZES with CCC and direct electrospun PVDF-TrFE nanofibrous mat is expected to have great potential to take a step toward the development of sustainable Net Zero Energy Community in the future.