This study investigates the influence of cooling rates on the structural evolution and mechanical properties of ultra-high-molecular-weight polyethylene/high-density polyethylene fibers by systematically varying cooling media from ambient air (f1) to room-temperature water (f5). A significant structural inversion was observed between the as-spun and drawn fiber stages: while slow cooling (f1) promotes thermodynamic crystallization to form large, stable grains and maximum initial crystallinity (54%), rapid quenching (f5) effectively “freezes” the molecular chains in a low-crystallinity, highly orientable precursor state by suppressing thermal relaxation. During subsequent hot-drawing, the quenched samples (f5) exhibited a superior response to tensile stress, achieving the highest maximum draw ratio due to reduced crystalline obstacles and enhanced chain mobility. This enables efficient stress-induced crystallization, leading to near-perfect crystal orientation (f_c > 0.95) and a dense microfibrillar framework. Consequently, the fiber performance trends reversed, with f5 achieving peak tensile strength (1.33 GPa) and modulus, whereas f1 remained limited by its rigid thermal history. These findings highlight that rapid quenching is essential for developing high-performance fibers by preserving a precursor structure that maximizes the potential of stress-induced crystallization.