Arabinoxylans (AXs) extracted from distillers dried grains with solubles (DDGSs) were treated with amylase, amyloglucosidase, and protease, to evaluate their effect on the polysaccharide capability to form covalent electro-sprayed nanoparticles. Enzymatically treated arabinoxylans (AXPPs) presented a significant decrease in protein content and molecular weight (31 and 37%, respectively), while the ferulic acid content and the arabinose-to-xylose ratio (A/X) were not statistically modified. The Fourier transform infrared spectra of the AXPPs showed a diminution in the intensity of amide I and amide II bands concerning AXs. The AXPP gels (1% w/v) induced via laccase registered a slight increase in the dimers of ferulic acid cross-linking content (9%) and the G’ value (27%) about the AX gels. The electro-sprayed nanoparticles of AXs and AXPPs (NAXs and NAXPPs, respectively) revealed a spherical and regular morphology via transmission electron microscopy. The nanoparticle diameter was not different for the NAXs and NAXPPs, while the NAXPPs show a significant reduction in Z potential value compared to NAXs. Confocal laser microscopy observations were conducted, to analyze the protein content in the AX network, and a decrease in illuminated areas was observed in the AXPP gels and the NAXPPs. These results indicate that the enzymatical treatment of an AX improves the polysaccharide gelling capability, but does not influence the fabrication of electro-sprayed covalent nanoparticles. NAXs and NAXPPs could be attractive biomaterials for diverse pharmaceutical and biomedical applications.