Abstract The inverted perovskite solar cells (PSCs) based on inorganic metal oxide hole transport layers (HTLs) bear the merits of high device stability and low material cost. However, the existence of metal‐vacancy defects on the surface of the metal oxide layer is a key constraint on achieving high efficiency and stability, like the case of the well‐known nickel oxide (NiO x ) HTL. Here, a cobalt oxide (CoO x ) HTL with the defect‐less surface is prepared by a solution process using Co(OH) 2 as the cobalt source and water as an eco‐friendly solvent for the first time. The PSCs based on CoO x HTL show superior thermal and ultraviolet stability over the conventional NiO x counterparts. Theoretical calculations reveal that CoO x has higher formation energy of metal‐vacancy defect as well as higher interfacial adhesion energy than NiO x , resulting in a chemically stable HTL/perovskite interface. After further manipulating the microstructure and the electronic properties of the CoO x HTL via magnesium acetate doping, a 22.35% efficiency is achieved with an ambient‐processed FA 0.4 MA 0.6 I 3 light‐absorbing layer. Such an efficiency exceeds all of the existing results reported for CoO x ‐based PSCs and a higher value of >24% is attainable via facile interface modification. The according device also demonstrates robust operational stability in the air without encapsulation.