The molecular mechanism of chain tilt in poly(ethylene terephthalate) (PET) fibers was proposed. The mechanism was considered basing on the ordering process from the cold drawn state of glassy PET. It was confirmed that the direction of maximum contraction on ordering agrees with the azimuth of chain tilt which varies with annealing temperature. In the stacking structure of irregular folded chain blocks of cold drawn PET, the expansion to the chain direction and the contraction to the lateral direction yield the compressive stress and tensile stress r respectively. The stress revealed as the result of the ordering from the glassy structure to crystalline structure can be relaxed by the rotation of the resulting crystallites. Therefore, we can suggest that the chain tilt is caused by the relaxation process of the stress.