Four-armed, star-shaped poly(D,L-lactide) (PDLLA) was synthesized and terminally-functionalized with either adenine or thymine complementary hydrogen bonding groups (PDLLA-A and PDLLA-T, respectively). The strong hydrogen bonding led to increased viscosity below the dissociation temperature of the hydrogen bonds. Rheology confirmed that these bonds were thermally reversible, with a sharp reduction in viscosity near 100 degrees C. PDLLA, PDLLA-A, and PDLLA-T were melt electrospun with no significant change in fiber diameter (all between 3.6 and 4.0 mu m). However, a blend of PDLLA-A and PDLLA-T formed fibers with an average diameter of 9.8 +/- 2.0 mu m, resulting from the hydrogen bond associations. Also, the phospholipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE) was melt electrospun at 200 degrees C and formed uniform fibers with average fiber diameter of 6.5 +/- 2.0 mu M.