Structural relaxation in a temperature range from 32 to 62° K glass transition has been investigated, for the first time, for a nearly monodisperse polystyrene using a differential scanning calorimeter and a thermal mechanical analyzer. Low temperature anneals in the vicinity of 320 K stabilize the glassy structure and lead to volume contraction. Upon heating, the annealed samples show an excess endothermic peak and exhibit a gradual expansion associated with structural recovery above the annealing temperature. Significantly, the samples recover the initial heat content and volume without reheating through the glass transition temperature. This sub‐Tgstructural relaxation behavior is in many respects distinct from that commonly observed near the glass transition. Kinetics of relaxation processes are also discussed.