Despite appealing supercapacitive properties, the flexible asymmetric supercapacitor devices (FASCs) are still suffering from low mass loading and limited operating voltage, leading to unsatisfactory energy densities. Herein, we introduced a high-voltage anodic electro-deposition process (AED) which is a novel avenue enabling the synthesis of hierarchical MnO2 on activated carbon cloth (H-MnO2/ACC). Interestingly, the concomitant activation of carbon cloth substrate is found to be beneficial to improve the conductivity and hydrophilic nature of our novel electrode. A FASC based on H-MnO2/ACC-300 and reduced carbon cloth (RCC) was assembled using a mixed ionic liquid gel (ionogel) electrolyte. Benefiting from highly conductive paths derived from intimately attached fiber-MnO2 interfaces, hierarchically interpenetrated lamella MnO2 porosity and concentric MnO2 interlayer voids, as well as the merits of ionic liquid, the resultant FASC delivers an output voltage as high as 4 V and an impressive volumetric energy density of 3.82 mWh/cm(3). Furthermore, the optimized H-MnO2/ACC-300 electrode with high mass loading can even retain 94.2% of initial capacitance upon 5000 cycles in 1 M Na2SO4. The unique H-MnO2/ACC can aid in the rational design towards flexible electronic devices with high mass loading and this synthetic strategy opens up enormous possibilities for the fabrication of electrodeposited materials.