This study investigates the unique morphology and mechanical properties of multi-jet electrospun cashew gum (CG) when combined with high molecular weight polyethylene oxide (PEO) and glycerol. Cashew gum (CG) is an inexpensive, non-toxic polysaccharide derived from Anacardium occidentale trees. Initially, the electrospinnability of aqueous solutions of cashew gum alone or in combination with PEO was evaluated. It was found that cashew gum alone was not suitable for electrospinning; thus, adding a small quantity of PEO was needed to create the necessary molecular entanglements for fiber formation. By using a single emitter with a CG:PEO ratio of 85:15, straight and smooth fibers with some defects were obtained. However, additional purification of the cashew gum solution and the incorporation of glycerol as a plasticizer were necessary to produce defect-free straight and smooth fibers. Interestingly, when the optimized formulation was electrospun using multiple simultaneous emitters, thicker aligned fiber bundles were achieved. Moreover, the resulting oriented fiber mats exhibited unexpectedly high elongation at break at ambient conditions. These findings highlight the potential of this bio-polysaccharide-based formulation for non-direct water contact applications requiring elastic properties.