In this study, a new method of preparing porous ultra-fine fibers via photo-crosslinking was developed. Ultra-fine poly(vinyl cinnamate)/ poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PVCi/PHBV) blend fibers were electrospun and then the PVCi was photo-crosslinked by UV irradiation. PVCi and PHBV were immiscible and the phase separation proceeded during the electrospirming process. After the photo-crosslinking of PVCi, PHBV was extracted from the blend fibers with chloroform. The average pore sizes in the remaining ultra-fine PVCi fibers were increased with increasing the content of PHBV in the ultra-fine PVCi/PHBV fibers. (C) 2005 Elsevier B.V. All rights reserved.