We present an experimental study of the emission characteristics and photonic band structure of a distributed feedback polymer laser, based on the material poly[${2\ensuremath{-}\mathrm{m}\mathrm{e}\mathrm{t}\mathrm{h}\mathrm{o}\mathrm{x}\mathrm{y}\ensuremath{-}5\ensuremath{-}(2}^{\ensuremath{'}}$-ethylhexyloxy)-1,4-phenylene vinylene]. We use measurements of the photonic band dispersion to explain how the substrate microstructure modifies both spontaneous and stimulated emission. The lasing structure exhibits a one-dimensional photonic band gap around 610 nm, with lasing occurring at one of the two associated band edges. The band edge (frequency) selection mechanism is found to be a difference in the level of output coupling of the modes associated with the two band edges. This is a feature of the second-order distributed feedback mechanism we have employed and is clearly evident in the measured photonic band structure.