Supercapacitors (SCs) using ammonium-ion (NH4+) as the charge carrier (NH4+-SCs) have attracted continuous attention and vanadium-based materials are proved to have high-efficient NH4+-storage properties. Monoclinic vanadium dioxide, VO2(B), as an anode material applied to SCs has been rarely reported and modulating its electronic structure for boosted NH4+-storage is full of challenge. In this work, molybdenum-doped VO2(B) (Mo-doped VO2(B)) is designed and synthesize to enhance its NH4+-storage. The introduction of Mo atom into the crystal structure of VO2(B) can modulate its crystal structure and bring in some defects. Experimental results manifest that Mo-doped VO2(B) with 2 % Mo-doping shows the best electrochemical properties. Mo-doped VO2(B) achieves the specific capacitance of 1403 F g−1 (390 mAh g−1) at 0.1 A g−1 and the capacitance retention of about 98 % after 5000 cycle, superior to that of VO2(B) (893 F g−1, 248 mAh g−1 at 0.1 A g−1 and 60 % capacitance retention. The hybrid supercapacitor (HSC) assembled by Mo-doped VO2(B) and active carbon delivers good electrochemical performance with the energy density of 38.6 Wh kg−1 at power density of 208.3 W kg−1. This work proves that the Mo-doping is an efficient strategy for boosted NH4+-storage of VO2(B) and this strategy is like a Chinese idiom “like adding wings to a tiger” to guide the design of electrode materials for high-efficient NH4+-storage.