Poly(arylene disulfide)s were prepared by thermo-initialized ring-opening polymerization (ROP) of macrocyclic(arylene disulfide) oligomers. These macrocyclic oligomers were synthesized by catalytic oxidation of 4,4-oxybis(benzenethiol) with oxygen in the presence of a copper-amine catalyst. This is the first work to characterize and investigate the electrical and mechanical properties of the poly(arylene disulfide)s obtained via ring-opening polymerization. The surface resistance and volume resistance of the polyaromatic disulfides cured at 180-220degreesC were higher than 10(14) ohm and 10(16) ohm (.) cm, respectively. The results indicated that the as-made polymers exhibited superior dielectric properties. Both mechanical strength and electrical properties of these polymers varied according to ROP conditions. These properties demonstrated that the macrocyclic(arylene disulfide) oligomers derived from 4,4-oxybis(benzenethiol) could be used to produce thermally curing insulating material to substitute epoxy resins. (C) 2005 Springer Science + Business Media, Inc.