This work covers the development of robust and stable in time poly[1-(trimethylsilyl)-1-propyne] (PTMSP) thin film composite (TFC) membranes with high CO2 permeance for its application in high pressure/temperature gasliquid membrane contactors used for amine-based solvents regeneration. For the first time, a novel technique of two-layers coating was proposed and successfully implemented to apply thin top-layer on microfiltration support by adjusting PTMSP solubility in organic solvents. By using different catalytic systems such as NbCl5 and TaCl5/TIBA, it was possible to synthesize two polymer samples ("PTMSP-Nb" and "PTMSP-Ta"), which are insoluble and soluble in hexane, respectively. The first intermediate layer made of "PTMSP-Nb" was cast on the microfiltration porous support from a toluene solution in order to form a PTMSP-coated porous support. The solution of "PTMSP-Ta" in n-hexane was used for subsequent formation of a thin defect-free selective layer (second layer). By using two commercial polymeric (MFFK-1) and metal-ceramic (MC) supports with high surface porosity of 85% and 60%, respectively, it was possible to fabricate the tailor-made TFC membranes "PTMSP/MFFK" (top-layer - 0.5 mu m) and "PTMSP/MC" (top-layer 1.2 mu m) with an initial CO2 permeance of 50 and 36.3 m(3)(STP)/(m(2) h bar), respectively, and CO2/N-2 selectivity of 3.5. A preliminary conditioning of the PTMSP/MC membrane at 100 degrees C for 100 h in air was applied for the accelerated relaxation of PTMSP top layer. The resulting robust PTMSP/MC TFC membranes still provided a high CO2 permeance of 1.6 m(3)(STP)/(m(2) h bar) (similar to 600 GPU) without a noticeable decline of membrane performance within the long-term gas permeation testing (at least 250 h) at 100 degrees C. The PTMSP/MC membranes were further successfully utilized in HPT MGD for regeneration of 50 wt% methyldiethanolamine (MDEA) at elevated temperature (100 degrees C) and pressures (up to 30 bar). A stable TFC membrane performance was demonstrated and no solvent leakage through the membranes was observed. (C) 2014 Elsevier B.V. All rights reserved.