Atactic and syndiotactic-rich poly(vinyl alcohol) fibers were prepared by gel spinning using ethylene glycol as a solvent. The mechanical properties of the fibers were independent of the degree of polymerization, although they were dependent on syndiotacticity. The amounts of tie molecules and the difference between the amounts of hydrogen bonds and microvoids determine the mechanical properties. The mechanical properties depended on the orientation of the segments in the amorphous parts. The entangled segments produced in the amorphous parts as a consequence of the difficulty of drawing were considered to form the voids and cracks, which grow to a banded structure.