Novel biodegradable polycaprolactone containing N,N′-bis (2-hydroxyethyl) methylamine ammonium propane sulfonate (PCL-APS) was synthesized by ring-opening polymerization. The resulting polymers were characterized by nuclear magnetic resonance spectrum (NMR), Fourier transform infrared (FTIR) spectroscopy, gel permeation chromatograph (GPC), differential scanning calorimetry (DSC), and water contact angle (WCA). These measurements showed that the APS unit was introduced into polymers. The hydrolysis of PCL-APS was evaluated by soaking the polymer membranes in a pH = 3.20 acid solution. The rate of weight loss was increased with the content of APS increasing in polymer. The compatibility of polymers were evaluated by platelet adhesion, hemolytic test, and activated partial thromboplastic time (APTT) and prothrombin time (PT) experiments. Results showed that adhered platelets deceased after introducing sulfobetaine as compared to the control PCL, little hemolysis took place on PCL-APS, and APTT of PCL-APS polymers was prolonged than that of control PCL. Therefore, polycaprolactone containing sulfobetaine is a promising biodegradable polymer with good blood compatibility. © 2011 Wiley Periodicals, Inc. J Biomed Mater Res Part A:, 2011.