In this work, polyvinilydene fluoride (PVDF) microcapsules were prepared by using combined emulsion and phase inversion techniques. With this method, microcapsules with different diameters and porosities have been obtained by just controlling the diameter of the membrane used during the preparation. Using a PVDF solution containing the oxidation catalyst ammonium molybdate (20 wt %), catalytic polymeric microcapsules with diameters ranging from 600 to 1,200 microm have been obtained. Characterization of catalytic microcapsules by means of SEM, BSE, and EDX analyses showed a uniform ammonium molybdate dispersion in the polymeric matrix. Catalytic microcapsules have been tested in the oxidation of aromatic primary alcohols to corresponding aldehydes. In the range 600-1,200 microm, the microcapsule diameter influences the formation of oxidation products: in particular, microcapsule diameters >900 microm slightly diminish the formation of aldehyde due to a beginning diffusion limitation. An interesting structure-reactivity behavior, induced by the interaction between the polymeric membrane and the substituted aromatic alcohol, has been observed.