Poly(thiourethane-urethane)s with varying amounts of sulphur were synthesised by a two-step polycondensation consisting of the sequential addition of 1,6-hexamethylene diisocyanate and bis(2-mercaptoethyl) ether in a poly(epsilon-caprolactone) diol solution. Polymers prepared had high weight-average molecular weight and typical microdomains separation, as shown by size-exclusion chromatography and thermal analysis. Polymer surfaces were characterized by X-ray photoelectron spectroscopy and atomic force microscopy. The quantification of thiol groups at the surface was assessed using a fluorescent assay. Thiol concentration ranged between 7 and 14 nmol/cm, and was directly related to the amount of sulphur introduced in the polymerization and the macromolecule chains orientation at the surfaces. A preliminary in vitro degradation study and a proliferation assay were performed. The poly(thiourethane-urethane)s may have important applications as biodegradable and biocompatible materials for cartilage and bone tissue engineering. The surface thiol groups add the prospect of further functionalization. This is an important benefit compared to biodegradable poly(urethane)s that usually present low biological activity.