The electrospinning behavior of a block copolymer of trimethylene carbonate (TMC) and e-caprolactone dissolved in N,N-dimethylformamide (DMF) and methylene chloride (MC) was studied. The effects of the blended solvent volume ratio, concentration, voltage, and tip-collector distance (TCD) on the morphology of the electrospun fibers were investigated by scanning electron microscopy. The results indicated that the diameter of the electrospun fibers decreased with a decreasing molar ratio of MC to DMF, but beads formed gradually. With a decreasing concentration of the solution, the fiber diameter decreased,at the same time, beads also appeared and changed from spindlelike to spherical. A higher voltage and larger TCD favored the formation of smaller diameter electrospun fibers. The results of differential scanning calorimetry and X-ray diffraction showed that the crystallinity and melting point of the electrospun fibers decreased when increasing the TMC content in the copolymer. Compared with the corresponding films, the crystallinity and melting point of the electrospun fibers were obviously increased. (c) 2005 Wiley Periodicals, Inc.