According to the demand for high-performance fibers for high-latitude ocean exploration and development, this paper selects representative products of high-performance liquid crystal fibers: thermotropic liquid crystal polymer fibers (TLCP) and poly p-phenylene terephthalamide (PPTA) fibers. Through a series of freeze–thaw (F–T) experiments for simulating a real, cold marine environment, we then measure the retention of mechanical properties of these two kinds of fibers. Before that, due to the difference in their chemical structures, we tested their Yang–Laplace contact angle (YLCA) and water absorption; the results suggested that PPTA fibers would absorb more moisture. Surprisingly, then, compared with thermotropic liquid crystal polymer (TLCP) fibers, the retention of the mechanical properties of poly p-phenylene terephthalamide (PPTA) fibers decreased by around 25% after the F–T experiments. The Fourier-transformed infrared (FT-IR) analysis, the attenuated total reflection (ATR) accessory analysis and the degree of crystal orientation measured by two-dimensional wide-angle X-ray diffraction (2D-WAXD) confirm that no changes in the chemical and the orientation structure of the crystal region of the fibers occurred after they underwent the F–T cycles. However, as observed by scanning electron microscopy (SEM), there are microcracks of various extents on the surface of the PPTA fibers, but they do not appear on the surface of TLCP fibers. It is obvious that these microcracks will lead to the loss of mechanical properties; we infer that the moisture absorbed by the PPTA fibers freezes below the freezing point, and the volume expansion of the ice causes the collapse of the microfibrillar structure. The two sorts of fibers subjected to the F–T experiments are immersed in a sodium chloride solution, and the amount of water infiltrated into the PPTA microfibrillar structure is evaluated according to the content of sodium ions in the fiber surface and subsurface layers through X-ray spectroscopy (EDS) elemental analysis. From the above analysis, we found that TLCP fibers can more effectively meet the operating standards of the severe and cold marine environment.