Mixed nanostructured transition metal-based complex materials with hierarchical and porous architectures, built from interconnected nano-building blocks, are considered as high-performance positive electrode materials in supercapacitors (SCs). Herein, zinc.nickel.iron phosphide(ZnNiFe-P) and Zn.Ni.Fe.hydroxide precursors (ZnNiFe-OH) were combined in a 3D hierarchical and porous structure (ZnNiFe-(P/OH)) to improve their durability and electrochemical activity by incorporating a dual ligand synergistic modulation strategy. The 3D ZnNiFe.(P/OH) architectures, comprising perfectly aligned nanosheet arrays (NSA), were successfully grown on Ni foam using a facile hydrothermal process followed by partial phosphorization. The dual-ligand ZnNiFe.(P/OH) electrode exhibited excellent specific capacitance/areal capacitance (1708 F g-1/5.64 F cm-2 for 1 A g-1), high rate performance (62% upto 15 A g-1) and good cycle life. Moreover, the ZnNiFe.(P/OH) NSA positive electrode was coupled with an activated carbon negative electrode to design an asymmetric supercapacitor device. The device delivered an excellent capacitance of 187 F g-1 at 0.8 A g-1, a superior energy density of ~58.4 W h kg-1 at 600 W kg-1, and an excellent power density of 11250 W kg-1 at 34.4 W h kg-1 while maintaining good cycling performance (88% after 5000 cycles).