This work extends a recent EPR study on light- driven electron and energy transfer in a self- assembled zinc porphyrin- pyridylfullerene (ZnP-PyrF) complex.(1) We report on a triplet line shape analysis of the photoexcited PyrF monomer and the ZnP- PyrF complex dissolved in isotropic and anisotropic matrixes of different polarity, namely, toluene, tetrahydrofuran (THF), and the nematic liquid crystals (LCs), E-7 and ZLI-4389. The line shape of the unbound (3)*PyrF obtained in both isotropic matrixes exhibits triplet parameters similar to those obtained for other monoadducts of C-60 under similar experimental conditions. On the other hand, (3)*PyrF oriented in the LCs shows a complicated line shape, which is attributed to two conformers: (a) an axial dominant (85%) configuration characterized by triplet parameters, similar to those obtained in the isotropic matrixes and (b) a bent configuration associated with spin density localized about the poles accompanied by sign reversal of the ZFS parameter D of the (3)*C-60 moiety. Further, since in both LCs the ZnP-PyrF complex mainly exhibits a conformation with axial symmetry, the differences between the electron and the energy transfer routes in each LC are attributed to their different polarity. This study reflects the strength of LC matrixes to serve as a topological tool, enabling us to determine the conformers' distribution and to differentiate between electron and energy transfer routes.