Poly(ethylene glycol) methacrylate (PEGMA) was introduced into a polyurethane (PU) solution in order to prepare hemocompatible electrospun membranes for potential application as small diameter vascular scaffolds. Crosslinked PU/PEGMA hybrid nanofibers were fabricated by a reactive electrospinning process with N,N'-methylenebisacrylamide (MBAm) as crosslinker and benzophenone (BP) as photoinitiator. The photoinduced polymerization and crosslinking reaction took place simultaneously during the electrospinning process. No significant difference in the membrane morphology was found by SEM when PEGMA content was less than 20 wt%. The crosslinked fibrous membranes of PU/PEGMA exhibit higher hydrophilicity and mechanical strength than PU membrane. These nanofibrous membranes are potential substitutes for artificial vascular scaffolds.