We present new results of temperature dependence of photoluminescence spectra carried out on poly-p-phenylene vinylene (PPV) and on PPV composite films with single-walled carbon nanotubes. By performing studies at different temperatures (87 and 300 K), we show that a distribution of conjugated PPV segments is needed to interpret experimental data. At the microscopic scale, such a distribution corresponds to the morphological picture of poorly packed short chain segments and well-packed ordered long chain segments. Within this scheme, a new interpretation emerges for explaining the specific behavior of the photoluminescence bands. In particular, the two most intense components of the photoluminescence spectra of PPV thermally converted at 300 degrees C (2.23 and 2.43 eV at 300 K) change drastically their relative intensity when the observation temperature decreases. This effect is interpreted as due to the inhibition of charge migration to longer segments and to radiative recombination occurring mainly on n = 5 conjugated segments.