The purpose of this investigation was to extract ferulated arabinoxylans (AX) from dried distillers’ grains with solubles (DDGS) plus to investigate their capability to form covalently cross-linked nanoparticles. AX registered 7.3 µg of ferulic acid/mg polysaccharide and molecular weight and intrinsic viscosity of 661 kDa and 149 mL/g, correspondingly. Fourier transform infrared spectroscopy (FTIR) was used to confirm the identity of this polysaccharide. AX formed laccase induced covalent gels at 1% (w/v), which registered an elastic modulus of 224 Pa and a content of FA dimers of 1.5 µg/mg polysaccharide. Scanning electron microscopy pictures of AX gels exhibited a microstructure resembling a rough honeycomb. AX formed covalently cross-linked nanoparticles (NAX) by coaxial electrospray. The average hydrodynamic diameter of NAX determined by dynamic light scattering was 328 nm. NAX presented a spherical and regular shape by transmission electron microscopy analysis. NAX may be an attractive material for pharmaceutical and biomedical applications and an option in sustainable DDGS use.