In the present study, the effects of drawing stress on poly(ethylene terephthalate) (PET)-chain extension prior to fiber-structure formation as well as the mechanical and thermomechanical properties of the resulting fiber were investigated. The amount, persistence length, and extension of molecular chains bearing external force were analyzed from the diffraction of the smectic phase observed after necking. For PET fiber with a molecular weight of 19,600 g/mol drawn at a stress lower than the critical value of 99 MPa, less d-spacing and less amount of the smectic phase, slower crystallization, and longer crystallization-induction time were observed. Furthermore, the critical stress value appeared to decrease with increasing molecular weight. When the drawing stress was less than the critical value, the d-spacing extrapolated immediately after necking decreased rapidly with decreasing drawing stress, and this decrease leads to a decrease in the tensile strength and thermal shrinkage of the drawn fiber.