Spin-dependent electron-hole (e-h) recombination in poly(p-phenylenevinylene) chains is modeled by the dissipative dynamics of the multilevel electronic system coupled to the phonon bath. The underlying Hamiltonian incorporates the Coulomb and exchange interactions of spin-singlet and spin-triplet monoexcitations in Wannier-orbital basis and their coupling to the prominent Franck-Condon active modes. In agreement with experiment, we obtain that the ratio of singlet versus triplet exciton formation rates is strongly conjugation-length dependent and increasing on going from the model dimer to the extended chain. The result is rationalized in terms of a cascade interconversion mechanism across the electronic levels. In parallel to the direct formation of spin-dependent excitons, e-h capture is found to generate long-lived charge-transfer states, whose further phonon-mediated relaxation to the bottom of the density of states is hindered by the near e-h symmetry of conjugated hydrocarbons. Being nearly spin independent, such states most likely form an intersystem crossing pre-equilibrium, from which the singlet e-h binding channel is about ten times faster than the triplet one. (C) 2003 American Institute of Physics.