A new procedure for the synthesis of porous and nonporous polyvinyl alcohol beads by controlled methanolysis of different concentrations of polyvinyl acetate suspension is described. By crosslinking with epichlorohydrin, insoluble crosslinked polyvinyl alcohol gels were obtained. These gels exhibit some peculiar swelling properties related to the reticulation degree, probably due to the interchain hydrogen associations. Crosslinked polyvinyl alcohol beads can be used as supports for liquid chromatography and for enzyme immobilization. Some new stationary phases for affinity chromatography and for ion-exchange chromatography were obtained. No substantial modifications in the catalytic properties of enzyme immobilized on crosslinked polyvinyl alcohol gels were established.