A room temperature thiol-ene click polymerization afforded a poly(ester sulfide) (M-n = 1.4-6.9 X 10(4)), which represents the first in a new class of click polyesters. Subsequent oxone oxidation of the poly(ester sulfide) led to the corresponding poly(ester sulfone), which had improved thermal stability in comparison with the parent poly(ester sulfide). A bioactive glass/poly(ester sulfone) composite could be deposited on a stainless-steel anode by electrophoretic deposition (EPD). Hydroxyapatite was found on the surface of electrophoreticafly deposited bioactive glass/poly(ester sulfone) composites that had been immersed in simulated body fluid (SBF) for 2 weeks. This bioactive glass/poly(ester sulfone) composite might therefore find use as a surface coating for implantable medical devices on which a hydroxyapatite layer can form post implantation to strengthen the interface between the implant and host bone.