Efficient protection of alcohols, phenols, amines, thiols and aldehydes has been carried out under catalysis by the highly active Preyssler heteropolyacid H 14 [NaP 5 W 29 MoO 110 ] (H 14 PMo). In this paper we report the catalytic activity of bulk H 14 PMo in each procedure to form: 2-tetrahydropyranyl acetals of alcohols and phenols, working at room temperature and using toluene as solvent; aldehyde 1,1-diacetates (acylals), a solvent-free preparation using Ac 2 O at room temperature; alcohol acetates, phenols, amines and thiols, working at room temperature, using toluene as solvent and Ac 2 O as acetylating agent; benzhydryl-ethers from the reaction of alcohols or phenols and diphenylmethanol, in toluene at 60–80°C; and silylation of phenol and alcohols with hexamethyldisilazane as silylating agent in toluene at 85°C.All the described procedures provide useful alternatives for performing the protection of different functional groups, which are general, rapid, selective and inexpensive, and have a low environmental impact. The catalyst was easily recovered and reusable in all of the described procedures, without loss of its catalytic activity.