In multi-step organic syntheses, the protection and deprotection of tetrahydropyranyl (THP) ethers is one of the most frequently used methods. Over the years, different methods have been used from various catalytic systems for the protection of hydroxyl groups as THP ethers and their deprotection. Herein we have reported that various alcohols and phenols have been efficiently converted to the corresponding THP ethers in high to excellent yields using catalytic amounts of ammonium decatungstocerate(IV) at room temperature. In the presence of this catalyst, various THP ethers have also been deprotected to the parent alcoholic or phenolic compounds. Mild reaction conditions, high to excellent yields, easy handling, compatibility with the other protecting groups and heterogeneous, non-toxic and cost-effective catalyst are some of the major advantages of this procedure. Because of its operational simplicity, generality, and efficacy, this method could be used for the conversion of various hydroxyl compounds to the corresponding THP ethers and vice-versa.