A new Na/Co-based heterometallic metal-organic framework, [Na2Co(SDCA)(mu(2)-OH)(2)(mu(2)-H2O)(2) (Azopy)](n) (where Azopy = 4,4'-Azopyridine and SDCA = 2,5'-thiophenedicarboxylic acid) (1) with nanorod-shaped morphology was synthesized using mixed-ligand approach via slow-diffusion technique under ambient conditions. The crystal structure study demonstrates the proportion of Co(II) and Na(I) metal node to be 1:2 and the acquired coordination network reveals as a 3D architecture. Topologically, the 4-c Na(I) ion directs in situ assembly of 4-c SDCA linker and 6-c Co(II) ion, resulting in the formation of 4,4,6-c net with a topology named as smm3. Additionally, 1 was incorporated as a binder-free material for a glassy carbon electrode (1-GCE) to explore its supercapacitor performance, which reveals a high specific capacitance of 321.8 F g(-1) at 4 A g(-1) and notable rate performance (similar to 78.9% of initial capacitance up to 16 A g(-1)) as well as excellent cycling stability (retains 97.4% after 5000 cycles). The demonstrated strategy of employing different heterometallic clusters with mixed ligands markedly increases MOF's complexity and induces synergistic properties, which is highly favorable for electrochemical applications. Hence, the present approach can be extended to build a wide range of MOFs and synergistically enhanced electrochemical performance can be achieved.