Zinc-based electrochemistry attracts significant attention for practical energy storage owing to its uniqueness in terms of low cost and high safety. In this work, we propose a 2.0-V high-voltage Zn–MnO
2
battery with core@shell Co
3
O
4
@MnO
2
on carbon cloth as a cathode, an optimized aqueous ZnSO
4
electrolyte with Mn
2+
additive, and a Zn metal anode. Benefitting from the architecture engineering of growing Co
3
O
4
nanorods on carbon cloth and subsequently deposited MnO
2
on Co
3
O
4
with a two-step hydrothermal method, the binder-free zinc-ion battery delivers a high power of 2384.7 W kg
−1
, a high capacity of 245.6 mAh g
−1
at 0.5 A g
−1
, and a high energy density of 212.8 Wh kg
−1
. It is found that the Mn
2+
cations are
in situ
converted to Mn
3
O
4
during electrochemical operations followed by a phase transition into electroactive MnO
2
in our battery system. The charge-storage mechanism of the MnO
2
-based cathode is Zn
2+
/Zn and H
+
insertion/extraction. This work shines light on designing multivalent cation-based battery devices with high output voltage, safety, and remarkable electrochemical performances.