The phase behavior of ternary blends of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO), polystyrene (PS) and a 50/50 mole % statistical copolymer of o-chlorostyrene and p-chlorostyrene [p(oClS-pClS)] has been investigated by differential scanning calorimetry (DSC) and analyzed in terms of a Flory-Huggins mean-field segmental interaction parameter treatment. Both PS/PPO and PPO/p(oClS-pClS) binary blends exhibit single glass transition temperatures over the full composition range whereas the PS/p(oClS-pClS) system displays a substantial immiscibilty window which extends into the ternary phase diagram. In principle, ternary systems provide enhanced opportunities relative to binary systems for evaluating segmental interaction parameters chi(ij)s from experimental data because of the high sensitivity of phase boundary locations to these parameters and to component molecular weights. In this system the effect of these parameters on the phase boundary was studied experimentally and compared to calculated values. (C) 2004 Elsevier Ltd. All rights reserved.