Dextran is soluble in both water and organic solvents, so it could be a versatile biomacromolecule for preparing nanofibrous electrospun membranes by blending with either water-soluble bioactive agents or hydrophobic biodegradable polymers for biomedical applications. We have formulated electrospun dextran membranes, and the effects of various processing parameters on the membrane properties were investigated. It was found that uniform nanofibrous dextran membranes could be formed by using water, DMSO/water, and DMSO/DMF mixtures as solvents through adjusting the processing conditions (solution concentration, voltage, and the distance between the electrode and the collecting plate). When water was used as a solvent, up to 10% (w/w) of bovine serum albumin (BSA) or lysozyme could be directly incorporated into the dextran electrospun membrane without compromising its morphology. No significant effect of the electrospinning process on lysozyme activity was observed. The composite electrospun membranes consisting of poly(D,L-lactide-co-glycolide) (PLGA) and dextran were obtained using DMSO/DMF (50/50, volume ratio) mixture as solvents. For cross-linking the electrospun membrane, dextran was modified by substitution of methacrylate groups at the hydroxyl sites. It was found that the electrospun membranes prepared from methacrylated dextran can be cured by UV irradiation in the presence of 1% of 2,2-dimethoxy-2-phenylacetophenone (DMPA) as a photoinitiator.