Polyurethanes (PUs) composed by hard and soft segments have been extensively used in the manufacturing of biocompatible prosthesis and medical devices. A broad variety of PUs can be obtained by modifying the balance between both segments. In the present work, different basically‐flexible PUs have been prepared by employing different combinations of aliphatic hexamethylene diisocyanate, poly(ethylene glycol) (Mw 400 Da), poly(ϵ‐caprolactone) diol (Mw 530 Da), and 1,4‐butanediol. Thermal analysis of the synthesized PUs demonstrated high thermal stability and the assumption of glassy state well below room temperature, in agreement with their marked flexibility. Morphological characterization of PUs films indicated that films prepared by spin coating were smoother and more homogeneous than those obtained by casting. Biological assays performed by using 3T3/BALB‐C mouse embryo fibroblast cell line confirmed the absence of toxicity and hence the biocompatibility of PU‐films.