We have studied the temporal and spectral evolution of the photoluminescence (PL) in a highly luminescent poly(2,5-bis(dimethyloctylsilyl)-1,4-phenylenevinylene) in the temperature range between 12 and 300 K using the ps time-resolved PL system. The PL spectra are narrower compared with an absorption spectrum and show a red-shift as time progresses after photoexcitation, implying that excitons are generated in a distribution of conjugation lengths and migrate towards longer conjugated segments.