Reinforcing polyoxomolybdates (POMs) into the activated carbon (AC) template engenders a nanohybrid electrode material for high-performance supercapacitor applications. Herein, a first-time novel integration of two polyoxometalates ([PVMo11O40]4-, [PV2Mo10O40]5-) with AC has been demonstrated, and their structural and electrochemical performances were analyzed. AC-VMo11 composite displayed an enhanced capacitance of 450 Fg-1 with an improved energy density of 59.7 Whkg-1. Furthermore, the symmetric supercapacitor cell for AC-VMo11 and AC-V2Mo10 showed high cell capacitances of 38.8 and 20.01 mF, respectively, alongside 99.99% capacitance retention of over 5000 cycles. In addition, the influence of ionic liquid as an electrolyte on AC-V2Mo10 based supercapacitor cell was investigated in tetrabutylammonium bromide (TBAB) electrolyte solution. © 2021 Elsevier Ltd and Techna Group S.r.l.