A vibrational analysis has been carried out to analyze the chain conformation of poly(lactic acid) in the crystalline state. In conjunction with a normal-coordinate analysis, the Raman spectrum has yielded data regarding conformational distributions. Raman spectra of different helices were simulated using previously published structures, force constants, and intensity parameters. Some of the chain conformations predicted are inconsistent with the data. Only one of the four 3(1) helical structures predicted by conformational analysis agrees well with experiment. This analysis provides a new understanding regarding the relative probability of a 10(3) or 3(1) helix for poly(lactic acid).