Solar conversion of CO₂ into energy-rich products is one of the sustainable solutions to lessen the global energy shortage and environmental crisis. Pitifully, it is still challenging to attain reliable and affordable CO₂ conversion. Herein, we demonstrate a facile one-pot approach to design core-triple shell Mn, C-codoped ZnO hollow spheres as efficient photocatalysts for CO₂ reduction. The Mn ions, with switchable valence states, function as “ionized cocatalyst” to promote the CO₂ adsorption and light harvesting of the system. Besides, they can capture photogenerated electrons from the conduction band of ZnO and provide the electrons for CO₂ reduction. This process is continuous due to the switchable valence states of Mn ions. Benefiting from such unique features, the prepared photocatalysts demonstrated fairly good CO₂ conversion performance. This work is endeavoured to shed light on the role of ionized cocatalyst towards sustainable energy production.