[Display omitted] • NZCS/3D Ni with the unique architectures contribute to Faradaic redox. • The mechanism study using the multimodal X-ray nanoprobe and electrochemistry. • Multimodal X-ray nanoprobe optimize the effect of synthesis parameters. • Multimodal X-ray nanoprobe is a great strategy for enhancing supercapacitance. The Ni-Zn-Co-S/3D Ni porous substrate was successfully synthesized and used as electrode material in supercapacitors. The morphology, structural characterization and supercapacitive performance of Ni-Zn-Co-S/3D Ni porous substrate can be controlled by adjusting the deposition time of 3D Ni porous substrate and the concentration of Zn-Co precursor solution. The Ni-Zn-Co-S/3D Ni porous substrate was characterized and investigated by SEM, TEM, XRD, XPS, and electrochemical analysis to expound their advantages and the mechanisms of energy storage/conversion processes. The results evidenced that Ni-Zn-Co-S/3D Ni porous substrate provided an effective strategy to significantly enhance the supercapacitive performance through the synergistic effect of unique interconnected architecture and redox characteristics of multiple metal oxides, which could create more electrochemically active sites for the fast redox reaction. These results also combined with X-ray spectroscopic technique (hard X-ray nanoprobe) gave us a better understanding to establish the optimization of the synthesis parameters for the preparation of electrode materials and could further provides useful insights for the future development and optimization of next-generation advanced energy storage/conversion technologies. [ABSTRACT FROM AUTHOR]