Electrospun fibrous mats were formed from linear and highly branched poly(urethane urea)s. The highly branched poly(urethane urea)s were synthesized using an A(2)+B-3 methodology, where the A(2) species is an oligomeric soft segment. Since the molecular weight of the A2 oligomer is above the entanglement molecular weight, the highly branched polymers formed electrospun fibers unlike typical hyperbranched polymers that do not entangle. Stress-strain experiments revealed superior elongation for the electrospun fibrous mats. In particular, the highly branched fiber mats did not fail at 1300% elongation, making the electrospun mats promising for potential applications where enhanced tear strength resistance is required. (c) 2005 Elsevier Ltd. All rights reserved.