Gum Arabic, known for its natural, biodegradable, and non-toxic attributes, holds significant promise in encapsulation. Despite the limited capacity of its natural form to create particles or fibers, this study aimed to produce nanocapsules through co-axial electrospraying, employing a solution of Gum Arabic/poly(vinyl alcohol) for the shell and Irgasan for the core. Additionally, process and solution parameters during co-axial electrospraying have been optimized. Solvent concentrations, total feed rates of shell/core solutions, needle tip to collector distance, electric field, and needle diameter have been studied in detail as a part of this optimization. Their effects on nanocapsule formation were observed through SEM images for morphological analyses and TEM images for observing capsule wall formation. The study thoroughly examines the properties of the resulting nanocapsules, reporting successful acquisition in the nano size range and monodispersity. This highlights the co-axial electrospraying method’s potential for the nanoencapsulation of Gum Arabic and Irgasan.