Electrospraying is a widely utilized technique for producing micro- and nanoparticles. This study examines the effects of gamma (γ) irradiation on the particle formation and size distribution of electrosprayed maize starch. Starch solutions were exposed to different irradiation doses (25–500 kGy) to evaluate its influence on polymer structure and electrospraying performance. Scanning electron microscopy and ImageJ software were used to assess particle morphology and size distribution, while Fourier-transform infrared spectroscopy was employed to analyze molecular modifications. The results indicated that γ irradiation significantly enhances particle formation, leading to a reduction in size between 51 and 112 nm with an improvement in uniformity at 200 kGy. Infrared spectroscopy analysis confirmed that gamma irradiation generated changes in the starch structure. These findings suggest that γ-irradiation serves as an effective modification technique for optimizing starch-based electrosprayed particles, enhancing their potential applications in drug delivery, food preservation, and medical applications.