Abstract In this work, we have theoretically investigated a model for the poly(2-methoxy-5(2'- ethylhexyloxy)-p-phenylenevinylene) (MEH-PPV) photodegradation based on structural models for MEH-PPV oligomers in vacuum and in solvent (chloroform). We investigated how the incorporation of oxygen and breaking of vinyl double bonds affect the absorption spectra. The theoretical results are in excellent agreement with the experimental data if we assume that the incorporation of carbonyl group is the main mechanism associated with the photodegradation processes.