The structure of freeze-dried atactic polystyrene (a-PS) prepared from benzene and cyclohexane dilute solutions (0.1 wt%) was investigated by Fourier transform infra-red spectroscopy. The freeze-dried a-PS showed infra-red absorption bands at 1047, 1098 and 1262 cm(-1) the last one had been reported for the 3/1 helical structure of isotactic PS in the crystalline state. It was revealed that the above absorption peaks correspond to some specific structure for the freeze-dried a-PS where the chain overlapping is absent in the glassy state. These absorption peaks were also found to be reduced by annealing above T-g, but not changed below T-g.