Polymer composite films of tris‐(8‐hydroxy‐quinoline) aluminum (Alq3) and polymethyl methacrylate (PMMA) at two different concentrations were investigated. Dielectric properties of the samples were measured in broad frequency range and results show an increase in specific conductance and susceptance by adding Alq3 in PMMA. Changes in dielectric spectra caused by irradiation of the samples with LED lamps at different wavelengths were also recorded. The samples were examined by UV–Vis and Fourier transform infrared spectroscopy. The interaction between Alq3 and the polymer matrix was observed in the photoluminescence spectroscopy spectra. The doping of the PMMA with different concentrations of the Alq3 leads to the unique photodielectric properties of the resulting composite, and that is the main result of this study. Due to its interesting optical and photodielectric properties, PMMA/Alq3 film may find application in solar cells and optoelectronics.

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