Efficient protection of alcohols, phenols, amines, thiols and aldehydes has been carried out under catalysis by the highly active Preyssler heteropolyacid H-14[NaP5W29MoO110] (H14PMo). In this paper we report the catalytic activity of bulk H14PMo 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 Ac2O at room temperature; alcohol acetates, phenols, amines and thiols, working at room temperature, using toluene as solvent and Ac2O as acetylating agent; benzhydryl-ethers from the reaction of alcohols or phenols and diphenylmethanol, in toluene at 60-80 degrees C; and silylation of phenol and alcohols with hexamethyldisilazane as silylating agent in toluene at 85 degrees 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. (C) 2010 Published by Elsevier B.V.