Pollock gelatin/poly(vinyl alcohol) (PVA) fibers were electrospun using deionized water as the solvent and pollock gelatin/poly(lactic acid) (PLA) fibers were electrospun using 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) as the solvent. The chemical, thermal, and thermal stability properties were examined for the electrospun samples. The electrospun PVA samples generally had thinner and more uniform fibers than the electrospun PLA samples. For the PVA samples, an increase in total solids content and PVA to gelatin ratio generally resulted in higher average fiber diameter values and wider diameter distributions. Pollock gelatin in both types of electrospun samples remained amorphous. The PVA in electrospun samples had comparable melting temperatures to that of neat PVA, whereas the PLA in electrospun samples had slightly lower melting temperatures than that of neat PLA. Also, the PLA in electrospun samples had crystallization temperatures approximately 30 °C lower than that in neat PLA. This was due to better alignment of PLA chains during electrospinning, which resulted in the chains being more readily crystallized at lower temperatures. In addition, the electrospun PVA samples completely dissolved in water at room temperature after soaking for one day, whereas the electrospun PLA samples remained intact even after soaking for three days.