The photoluminescence (PL) properties of thin films of the conjugated polymer [poly(2,5-bis(2'-ethyl-hexyl)-1,4-phenylenevinylene] have been investigated. At low temperatures the PL spectra show a narrow peak for the electronic transition and a series of well defined vibronic sidebands, which clearly reveal the electron coupling with two different vibronic modes. The purely electronic transition peak is observed to be very asymmetric so that it cannot be adjusted by a single Lorentzian or Gaussian function. In order to understand and explain this asymmetry we have considered a model where the purely electronic transition line shape is partially generated by a broadened square-root singularity representing one-dimensional electron states, and partially by localized (zero-dimensional) states. The localized states are assumed to be those very close to the band edges and are represented in our model by a single Gaussian function. Numerical Franck-Condon analysis was performed, resulting in a very good agreement between the theoretical and the experimental emission spectra. This procedure has confirmed the one-dimensional character of the electron states as the basis for the understanding of the purely electronic line shape asymmetry in the PL spectra of conjugated polymers at low temperatures. (C) 2004 American Institute of Physics.