[en] Highlights: • Photopolymerization of the {Pt(dbdtc)₂}·C₆₀ fullerene complex. • Decomposition kinetics of the photo-oligomers upon thermal treatment. • Extraction of the activation energy for the photo-oligomers’ decomposition. The photopolymer formation in the fullerene layers of the C₆₀ complex with platinum dibenzyldithiocarbamate is reported for the first time. The photo-oligomer peaks appear in the Raman spectra near the A_g(2) mode of the C₆₀ molecule upon sample illumination with various laser wavelengths. The photo-oligomers are unstable upon heating and revert back to the C₆₀ monomeric state. The activation energy of the thermal decomposition, obtained from the Arrhenius dependence of the decay time constant on temperature, is (1.12 ± 0.11) eV and the photo-oligomers decompose at ∼130 °C, being more fragile than the crystalline polymers of C₆₀.