Deuteron relaxation times T1 of polystyrenes deuterated at the backbone (PS-d3) and the phenyl ring (PS-d5), respectively, have been measured in solutions of benzene and diethyl malonate as a function of concentration and temperature. We conclude that the motion of the phenyl ring is faster than that of the backbone, the difference being smallest at high temperatures around 180°C. The temperatures dependence is discussed in relation to the activation energies in polystyrene.