Rechargeable zinc-ion batteries (ZIBs) have received wide attentiveness nowadays due to having several functional superiorities such as high energy density, cost-effectiveness, lesser toxicity, environmental benignity, and superior safety. Herein, we evaluated the potentiality of a 3D highly porous MIL-100(V) MOF as an efficient cathode material in ZIB. The constructed framework exhibited a maximum specific capacity of ∼362 mA h g−1 at 0.2 A g−1 current density and retained ∼ 95.45% initial capacitance with no significant loss of coulombic efficiency (CE) even after 3500 consecutive cycles. Moreover, the MIL-100(V)//Zn CR-2032-coin cell delivered high energy density of ∼ 195 W h kg−1 at 0.2 A g−1 current density, which could be attributed to the efficient immobilization of Zn2+ ions within the confined pore channels. Mechanism investigation of the Zn2+-storage/release process was verified by several ex-situ studies. A real-time experiment and slow zinc dendrite formation made MIL-100(V) MOF promising for next-generation energy storage devices.