The direct wet-spinning of syndiotacticity-rich poly(vinyl alcohol) from ammonolysis solutions of poly(vinyl trifluoroacetate) was carried out. The high draft in spinning could not be accomplished at lower and higher polymer concentration, but it was accomplished at a certain middle polymer concentration. The drawn fibers with high draft have not always high strength. The fibers with high strength were obtained from fibers wound at moderate draft in spinning and then drawn at higher times without solvent. The strength was independent on the degree of polymerization (in a range from DP = 1870 to DP = 5580), but it became higher in the case of thinner fibers obtained from the solutions of lower polymer concentration. Here, the highest Young's modulus and strength at break were 13.8 GPa and 12 gr/denier, respectively.