Poly(9.9'-di-n-hexyl-2,7-fluorenylenevinylene) (PDHFV) was synthesized with dibromodihexylfluorene and divinvidihexylfluorene by employing a Heck reaction with a palladium catalyst. The UV-visible absorption maximum at 400 nm from the polymer solution in chloroform has redshifted by 40 nm for the polymer film. The photoluminescence (PL) spectrum of the film showed the emission maximum at 470 nm with a strong excimer emission at 535 nm. The ratio of the excimer emission intensity to that of the singlet decay was constant regardless of the excitation energy. However, the indirect excitation of the fluorophore for the PL emission of a polymer blend at 470 nm was greatly enhanced at the expense of the excimer emission intensity.