A reflexive interface was designed and prepared based on poly(trimethylene carbonate) (PTMC), which was polymerized from the hydroxyl groups of cholesterol or poly(ethylene glycol) monomethyl ether (mPEG) by conventional ring-opening polymerization techniques. Resulting polymer coatings were analyzed in terms of surface wettability and polymer weight loss during degradation using contact angle and quartz crystal microbalance measurements. The adsorption of hydrophilic and hydrophobic dyes on the membrane was evaluated by UV-vis spectrometry and was found to be largely dependent on the polarity of the terminal unit such as the cholesterol or mPEG segment. For example, mPEG (M-n = 5000 g/mol)-PTMC membranes, abundant with surface mPEG segments, demonstrated quick, spontaneous surface enrichment in water. In terms of results, surface wettability increased and enzymatic degradation decreased due to a lack of enzymatic accessibility. Moreover, such membranes could adsorb hydrophobic dyes from aqueous solutions, demonstrating interfacial stabilization by mPEG segments. Resulting polymers could be interesting candidates for commercial applications and of specific interest in biomedical applications.