Layered materials including metal phosphates and phosphonates have been widely investigated in several fields acting as good selective catalysts in a great number of oxidative reactions. Zirconium phosphate amorphous [Zr(HPO4)(2)center dot H2O; ZrPA], sodium exchanged zirconium phosphate amorphous [Zr(NaPO4)(2); NaZrPA], potassium exchanged zirconium phosphate amorphous [Zr(KPO4)(2); KZrPA], zirconium phenylphosphonate amorphous [Zr(O3PC6H5)(2); ZrPPA], zirconium carboxyethylphosphonate [Zr(O3PCH2CH2COOH)(2); ZrCEP] and aluminium carboxyethylphosphonate [Al-3(OH)(3)(O3PCH2CH2CO2)(2)center dot 3H(2)O; AlCEP] were prepared, characterized and evaluated as selective catalysts in the Baeyer-Villiger oxidation of cyclopentanone, p-methoxybenzaldehyde and 2,4,6-trimethylbenzaldehyde by hydrogen peroxide, in acetic acid. The selectivity of delta-valerolactone, p-methoxyphenol and 2,4,6-trimethylphenol have been found to be strongly related with the properties and structure of each catalyst.