We report the two-photon fluorescence excitation spectrum of poly(p-phenylenevinylene) over the energy range 1.1-2.0 eV. The onset for two-photon fluorescence excitation is at 1.3 eV with a strong peak near 1.475 eV. The peak locates the energy of the lowest even parity excited singlet at 2.95 eV, some 0.5 eV above the lowest dipole-allowed singlet transition (the fundamental ππ* absorption). This energetic ordering of excited states is in agreement with the predictions of theory and is consistent with the strong one-photon fluorescence seen for this polymer. © 1993.