New thermoplastic polyurethane elastomers (TPUs) were synthesized by a one-step melt polyaddition from poly(oxytetramethylene) diol of M¯n = 2000 g/mol as the soft segment, 1,1’-methanediylbis(4-isocyanatocyclohexane) (HMDI, Desmodur W®), and 2,2’-[methanediylbis(benzene-4,1-diylmethanediylsulfanediyl)]diethanol (diol E) or 6,6’-[methanediylbis(benzene-4,1-diylmethanediylsulfanediyl)]dihexane-1-ol (diol H) as unconventional chain extenders. The effects of the kind and amount of the polymer diol and chain extender used on the structure and properties of the polymers were studied. The polymers were examined by Fourier transform infrared spectroscopy, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, Shore hardness and tensile testing. Both the adhesive and optical properties were determinated for a selected polymer. The obtained TPUs were amorphous, colorless, high-molar-mass materials. It was observed that the polymers with the diol E showed higher hardness and tensile strengths but smaller elongations at break than diol H-based ones. All of the polymers exhibited a relatively good thermal stability. Their temperatures of 5% mass loss were in the range 312-338°C.