We report the observation of electroluminescence and photoluminescence from microcavity structures containing poly(2,5‐dialkoxy‐p‐phenylene vinylene) (PDAOPV) conjugated polymer emitting regions. Strong spectral narrowing from 112 nm full width half‐maximum to 34 nm in electroluminescence and from 128 to 16 nm in photoluminescence and clear angular dependence of the peak emission wavelength are observed. These are characteristic signatures of the modification of spontaneous emission properties in microcavity structures.