Nowadays self-charging memristors and photodetectors open the path for future research into energy-autonomous electronics which hold the promise of enabling exceptionally efficient applications in memory storage, small portable electronics, neuromorphic computing, and optoelectronics devices. Hence, in the recent era, much research work has been focused on the development of nanogenerators for technological applications. In this regard, the main aim of the present study is to develop a multi-functional piezoelectric nanogenerator based on relaxor ferroelectric materials having three-phase MWCNTs/BSTO/PVDF nanocomposites. BSTO and CNT fillers promote >80 % electroactive phase nucleation in PVDF, making it appropriate for piezoelectric energy harvesting devices. Incorporating conductive fillers (CNTs) and dielectric fillers (BSTO) into the PVDF matrix enhances the piezoelectric nanogenerator's dielectric, ferroelectric, and output performance. PENG based on an optimized BSTO-CNTs-PVDF composite (with 20 % BSTO and 0.20 % CNTs loading) produced an output power of 31.5 µW with a high open-circuit voltage of 42 V and a short-circuit current of 9 µA, it demonstrates enough capability to power up small portable electronic devices. This work can also be used for a realistic technique for generating self-powered memristors and photodetectors for extremely efficient memristive neural networks and optoelectronics devices. Demonstration of power generation of the prepared device by different activities is demonstrated.