The photodegradation of poly(vinyl alcohol) (PVA) in aqueous solution was investigated under UV exposure and pulsed-laser irradiation. The degradation under UV exposure was studied at different pH values and with the addition of potassium chloride and potassium dichromate. The pulsed-laser degradation of PVA was investigated with a Nd : YAG laser, operating at a wavelength of 266 nm with about 6-ns pulses. The pulsed-laser degradation was studied at different polymer concentrations and light intensities. Samples were analyzed by gel permeation chromatography. The degradation rate coefficients were determined by the application of a continuous distribution model. The photodegradation rates under UV exposure were highest at extremes of pH and were greatly enhanced by the addition of potassium chloride and potassium dichromate. The pulsed-laser degradation of the polymer decreased with increasing polymer concentration, although a threshold light intensity was required to initiate the degradation process. © 2006 Wiley Periodicals, Inc.