Electrospun fibrous scaffolds are being developed for the engineering of numerous tissues. Advantages of electrospun scaffolds include file similarity in fiber diameter to elements of the native extracellular matrix and the ability to align fibers within the scaffold to control and direct cellular interactions and matrix deposition. To further expand the range of properties available in fibrous scaffolds, we developed a process to electrospin photocrosslinkable macromers from a library of multifunctional poly(beta-amino ester)s. In this study, we utilized one macromer (A6) from this library for initial examination of fibrous scaffold formation. A carrier polymer [poly(ethylene oxide) (PEO)] Was used for fiber formation because of limitations in electrospinning A6 alone. Various ratios of A6 and PEO were successfully electrospun and influenced the scaffold fiber diameter and appearance. When electrospun with a photoinitiator and exposed to light, the macromers crosslinked rapidly to high double bond conversions and fibrous scaffolds displayed higher elastic moduli compared to uncrosslinked scaffolds. When these fibers were deposited onto a rotating mandrel and crosslinked, organized fibrous scaffolds were obtained, which possessed higher moduli (similar to 4-fold) in the fiber direction than perpendicolar to the fiber direction, as well as higher moduli (similar to 12-fold) than that of nonaligned crosslinked scaffolds. With exposure to water, a significant mass loss and a decrease in mechanical properties were observed, correlating to a rapid initial loss of PEO which reached an equilibrium after 7 days. Overall, these results present a process that allows for formation of fibrous scaffolds from a wide variety of possible photocrosslinkable macromers, increasing the diversity and range of properties achievable in fibrous scaffolds for tissue regeneration. (C) 2008 Wiley Periodicals, Inc. J Biomed Mater Res 87A: 1034-1043, 2008