Abstract Poly(ɛ-caprolactone) (PCL) films were doped with photoactive 1,2-diphenylethane-1,2-dione (benzil, BZ), and the effect of the photochemical transformation of benzil on the molecular characteristics of the PCL films and the rate of PCL hydrolysis was studied. Both crosslinking and degradation of the PCL film were observed during irradiation of the PCL/BZ films. Irradiation of a PCL/BZ film at λ > 400 nm under an air atmosphere resulted in a decrease of the average molecular weight (Mn) of PCL to approximately one half, while formation of polar groups and an increase in the hydrophilicity of the PCL film were observed. Moreover, a subsequent hydrolytic test showed a significant increase in the hydrolytic degradation rate of the PCL/BZ film in comparison with non-irradiated or irradiated PCL films without doped benzil. Using benzil as a dopant in the PCL matrix can allow adjusting the degradation rate of PCL, what can be very important from both environmental and biomedical perspectives.