Complexes of polyvinylpyrrolidone-polyacrylic acid (PVP-PAA) photo-polymerized from a mixture of PVP and acrylic acid (AA) were characterized by means of differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectrometry. The swelling of PVP-PAA semi-interpenetrating network (semi-IPN) films was studied in various pH media. The results showed that swelling in 0.1N HCl solution and pH 3.0 phosphate buffer was strikingly different from that in the pH 6.0 phosphate buffer. Caffeine release rate from the semi-IPN film followed Fick＇s Law. The rate of release was higher in dissolution media having pH above a critical value of about 3.8. Control of caffeine release from the semi-IPN film was realized by changing cyclically the pH of dissolution medium between 0.1N HCl solution and pH 6.0 phosphate buffer.