Shape memory polyurethanes (SMPUs) were prepared from polycaprolactone diol 4000 (PCL 4000), 4,4′-diphenylmethane diisocyanate (MDI), 1,4-butanediol (BDO), chitin, dimethylol propionic acid (DMPA), and triethylamine (TEA). The synthesized samples were irradiated for 50, 100, and 200 h in an UV exposure unit. The effects of chitin and DMPA contents in the polyurethane (PU) formulation on surface properties of the UV-irradiated PU samples were investigated by contact angle measurements, surface free energy and water absorption (%), total work of water adhesion to polymer and equilibrium degree of swelling. Results of the aforementioned surface techniques revealed that the UV-irradiated PU samples were affected by varying the UV exposure period. The interactions of the PU films with solvents on the surface were clearly related to the contents of DMPA and chitin in the final polyurethane formulation and UV-irradiation time.