Harnessing the power of contact electrification, triboelectric nanogenerators (TENGs) are a cutting-edge energy technology, where output performance is greatly influenced by the micro/nano scale architectures of triboelectric layers. We present a study on the development of TENG by introducing an advanced 3D hierarchical microcubic morphological structure prepared by simple solution casting method, employing a renewable material, lignin, in combination with eco-friendly polyvinyl alcohol (PVA) matrix. The strategic incorporation of epichlorohydrin (EPCH) as a crosslinker enhances thermal stability, and crosslinking within the lignin/PVA composite (LPC) film. A remarkable outcome of this integration is the emergence of a 3D hierarchical microcubic structure within the LPC film. This structure, with its intricate 3D arrangement, emerges as the cornerstone that underpins the development of LPC-TENGs devices distinguished by their simple fabrication process, elevated output performance, and multifaceted applications. The LPC-TENG, adorned with its unique 3D hierarchical microcubic architecture, establishes new standards in energy harvesting and sensing capabilities with a maximum output power density of 135.4 mWm−2, a short-circuit current of 6.44 μA, and a maximum output voltage of 65 V (5 times higher than PVA-based TENGs). Additionally, the LPC-TENG showed exceptional performance as a self-powered bifunctional sensing system, providing a steady output voltage range of 0–10 V across various humidity levels (20–90 % RH) and a wide usable pressure range (0–162 kPa) with a low detection limit of 1 kPa. We demonstrated the application of the LPC-TENG in energy harvesting from human walking, enabling simultaneous measurements of environmental relative humidity, pressure, and illumination of 27 commercial LEDs. The unique 3D hierarchical microcubic architecture offers an unparalleled foundation for accommodating overall performance and diverse sensing functionalities.