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The transient photoluminescence (PL) of DO-PPV (poly-(2,5-dioctyloxy-1,4-phenylene vinylene)) solution in chloroform was investigated by picosecond time-resolved PL spectroscopy. An ultrafast rise of PL and the following single exponential decay with a time constant of about 400ps were assigned to the formation of the intrachain exciton and its decay process, respectively. The redshift of the PL emission spectrum with time was caused by the subsequent exciton migration among the different conjugated segments in the DO-PPV polymer.