Plasma polymers are often limited by their susceptibility to spontaneous and photo-oxidation. We show that the unusual photoluminescence (PL) behavior of a plasma polymer of trans-2-butene is correlated with its PL strength. These photoprocesses occur under blue light illumination (l ¼ 405 nm), distinguishing them from traditional ultraviolet degradation of polymers. These photo-active defects are likely formed during the plasma deposition process, and we show that a polymer synthesized using initiated (i)CVD, a non-plasma method, has 1000Â lower PL signal and enhanced photo-stability. Nonplasma methods, such as iCVD, may therefore be a route to overcoming material aging issues that limit the adoption of plasma polymers.