The relaxation and dynamics properties of paramagnetic centers formed at irradiation of C60/triphenylamine (TPA) crystalline complexes were investigated at 3-cm and 2-mm waveabnds EPR. C60/TPA crystals was found to rotate activately at low temperatures. The rate of this motion increases sharply at 260 K due to a phase transition. It is accompanied with the change in electron relaxation and paramagnetic susceptibility of the system. Molecular motion is determined by the elemental unit size and by TPA conformation. Two types of paramagnetic centers with single and triple states was shown to exist in the system.