Ozone has gradually become a kind of air pollutant that can not be ignored. A highly efficient and stable catalyst for ozone decomposition in humid environments is still a challenge. This paper used a series of novel phosphate catalysts in the ozone field. With the increase of Ni Content in Co(3−x)Ni(x)(PO4)2, crystal formation in Co(3−x)Ni(x)(PO4)2, but excessive Ni destroyed the lattice structure of Co(3−x)Ni(x)(PO4)2 which becomes amorphous. As a result, the specific surface area of materials has an obvious enlargement along with an increase of the surface oxygen content from crystal to amorphous, which is beneficial for improving its active sites on the catalyst. At a condition of relative humidity (RH)= 65 %, Co(3−x)Ni(x)(PO4)2 exhibited outstanding catalytic activity and stability at room temperature. Most importantly, Co1.8Ni1.2PO4 could degrade O3 against the influence of water vapor at RH of 90 %. The research shows the development prospect of phosphate in the field of efficient catalytic decomposition of ozone.