Abstract The changes in the electronic absorption spectra (UV–Vis) of ferrocene-doped poly(methylmethacrylate) (PMMA) thin films, containing chloroform molecules as impurities, after photoexcitations in air as well as in dry nitrogen atmosphere have been investigated. Photoexcitations have been made by monochromatic radiation (using a Xe-lamp source and a monochromator) at an interval of few nanometers in the spectral range 210–750 nm. The changes in spectra after photoexcitation have been studied as a function of: (i) time (duration) of photoexcitation; (ii) amount of ferrocene in the film; and (iii) amount of chloroform molecules in the film. The analysis of the results has indicated the occurrence of photoinduced charge-transfer between ferrocene and chloroform molecules confined in the PMMA thin films. The action spectrum of photoinduced changes has shown one peak in the UV region at about 261 nm. Ferrocene-doped PMMA thin films containing chloroform molecules are expected to be useful in the photoelectrochemical devices.