One of the principal failures of current vascular prostheses is compliant mismatch between the host arteries and prostheses at the anastomoses. Current commercial vascular prostheses are fabricated using either microporous poly(tetrafluoroethylene) or poly(ethylene terephthalate), both of which are incompliant in comparison with the host artery. Thermoplastic polyurethanes that are inherently compliant, therefore, offer the potential for use as vascular prostheses. This article presents a new approach to produce a compliant microporous thermoplastic polyurethane material using a coagulation coating technique. A study on the factors affecting the physical and structural behaviors based on porous polyurethane membranes were investigated. The effects of coagulants and coagulation temperatures on the properties of the coagulums were evaluated and the mechanism for the formation of microcellular structures was discussed.