Angle-resolved photofragmentation of the N K-shell excited CF3CN molecule was studied by using a time-of-flight mass spectrometer. The anisotropy parameter(beta) values for CF3+, CF2+ and CN+ fragments with kinetic energies were close to - 1 at the excitation of the N(ls) electron to the resonant pi(CN)(*) state. That is, these energetic fragment ions were ejected in a direction perpendicular to the linearly polarized electric vector of the photon beam. Angle-dependent fragmentation was not observed by the photoexcitation of the N(ls) electron to the sigma(CN)(*) state.