This work presents the first part of our study on the modification of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) with styrenic thermoplastic rubbers. Polystyrene-b-polyisobutylene-b-polystyrene (SIBS), polystyrene-b-polybutadiene-b-polystyrene (SBS) and polystyrene-b-poly-(ethylene/butylene)-b-polystyrene (SEBS) triblock copolymers were melt blended with PPO and the blends were characterized. Differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and transmission electron microscopic (TEM) studies revealed that PPO/SEBS blends displayed the most pronounced phase-separated morphology with largest rubbery domains. SBS showed the most miscibility, and the least detrimental effect on dynamic mechanical properties and tensile strength. The results of this comparative study guided us to develop optimum conditions for the impact modification of PPO by SIBS thermoplastic rubbers. (c) 2006 Elsevier Ltd. All rights reserved.