Poly(L-phenyllactic acid)s (PLPhLAs) with high molecular weight were prepared by a direct polycondensation of L-phenyllactic acid in the presence of stable Lewis acids such as HfCl4 center dot 2THF under various reaction conditions. As a result, PLPhLAs with a number-average molecular weight (M-n) more than 100000 g mol(-1) were obtained and showed specific optical rotation [alpha](D)(25) of -46 degrees and the glass-transition temperature (T-g) of 55 degrees C whose absolute values were higher than the reported values and was comparable with T-g of poly(L-lactic acid).