The photodegradation mechanism and luminescence efficiency of a series of thin polymer films prepared under a variety of conditions was studied. The conjugated polymer, poly(m-phenylene-co-2,5-dioctoxy-p-phenylenevinylene) (PmPV), is shown by infra-red spectroscopy to degrade via the chain scission of the carbon double bond along the polymer backbone. This causes a reduction in conjugation length and a blue shift in its absorption and photoluminescence (PL) spectra. To reduce photadegradation effects, films were prepared using argon (Ar) gas and were investigated in air and an oxygen free environment. The initial PL intensity increased by over 70% for Ar treated films. The PL decay in air was bi-exponential in nature, with a sharp initial decay linked to atmospheric oxygen, and a longer second decay linked to oxygen embedded in the film. The increase in both PL efficiency and degradation lifetime, coupled with device encapsulation, should significantly improve the performance of electroluminescent devices.