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Direct melt/solid polycondensation of lactic acid (LA) was carried out to obtain high molecular weight poly(lactic acid) (PLA) by a process using various catalysts in the first-step melt polycondensation, and followed solid polycondensation by using p-toulenesulfonic acid monohydrate (TSA) as the catalyst in the second step. Effects of various catalysts and reaction temperature on the molecular weight and crystallinity of resulting PLA polymers were examined. It was shown that SnCl2·2H2O/TSA, SnCl2·2H2O/succinic anhydride, and SnCl2·2H2O/maleic anhydride binary catalysts should be effective binary catalysts to obtain high molecular weight PLA of more than 1.2 × 105. A conventional melt spinning method was used to spin PLA fibers, which displayed tensile strength of (382.76 ± 1.41) MPa and tensile modulus of (4.36 ± 0.07) GPa.