Extended thermal annealing treatments were used to modify the B-site cation order in the (1 - x)PMN–xPSN perovskite system (where PMN is lead magnesium niobate, Pb(Mg1/3Nb2/3)O3, and PSN is lead scandium niobate, Pb(Sc1/2Nb1/2)O3). Extensive 1:1 ordering could be induced in compositions with x ≧ 0.1. The substitution of PSN into PMN produced a large increase in the thermal stability of the 1:1 ordered phase, with the maximum disordering temperature of ~1360oC being observed for the x = 0.5 composition. By monitoring the change in the degree of order with temperature, the order–disorder boundary for the PMN–PSN system was established and the transition temperature for pure PMN was estimated to be ~950oC. The changes in stability across the system were consistent with the "random-site" description of the cation order. The change in enthalpy associated with the ordering was affected by the size difference of the two ordered cation sites and by the size and charge mismatch of the metal cations that occupy the random-site position.