Structurally different poly(arylene ether sulphone) (PES) copolymers were synthesized by reacting stoichiometric amount of dichlorodiphenyl sulphone (DCDPS) with bisphenols. The molar ratio of bisphenol-A and phenolphthalein (ESP)/hydroquinone (ESH)/resorcinol (ESR) was varied to prepare nine copolymer samples. Structural characterization was done by FT-IR and 1H-NMR studies. The initial decomposition temperature as well as temperature of maximum rate of mass loss in ESR and ESH copolymers were similar and a marginal decrease in these decomposition temperatures were observed by increasing the isopropylidine units in the backbone. High char residue at 800C was observed in polymers having high content of phthalein units.