Soluble and thermally stable polycarbonate polyurethane elastomers were synthesized through a solvent‐free and nonisocyanate melt transesterification process. The conditions of this process were studied, and the optimum conditions were as follows: the catalyst dibutyltin oxide dosage was 0.125 wt %, the raw material molar (n) ratio of dimethyl 1,6‐hexamethylene dicarbamate (HDC) to poly(carbonate macrodiol) (PCDL) was n(HDC)/n(PCDL) = 1:0.99, the reactants were prepolymerized under 100°C for 1 h and then under 185°C and a high vacuum for 4 h. Three different PCDLs were selected to participate in the reaction under the conditions mentioned previously, and their structures were characterized by Fourier transform infrared spectroscopy and X‐ray diffraction. The products obtained from this process were still stable under 280°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41377.