Excimer conformation of a novel poly(2-vinylpyrene) (P2VPy) was studied by fluorescence spectra and decay measurements in 2-methyltetrahydrofuran solution. The pyrene chromophores of this P2VPy are substituted at the C-2-symmetry position, and hence formation of only the full-overlap excimer is possible. The excimer emission of P2VPy was compared with that of poly(1-vinylpyrene), in which the pyrene group is able to form both full- and partial-overlap excimers. The excimer emission spectra of both polymers were very similar at room temperature, whereas at low temperatures a large difference between the emission intensities was observed due to the full-overlap excimer formation of P2VPy.