Ultragriseofulvin (UGF) is an antifungal drug classified as a class II drug with poor solubility and high permeability, where the dissolution rate is the primary limiting step of its absorption. The present study aimed at enhancing the dissolution rate of UGF by high voltage-based solvent evaporation technique forming Amorphous Solid Dispersions (ASDs) with the modified polyethylene glycol grafted copolymer, Soluplus® (SOL). Conventional, electrospun, and electrosprayed ASDs of UGF and SOL were prepared, characterized, and their in-vitro dissolution rates were studied. Electrosprayed UGF/SOL composites prepared in a ratio of (1:4) in a mixed solvent (DMF: DCM, 1 : 1, w/w), under (15.3 Kv) voltage produced NPs with an average particle size of 139.23 ± 17.70 nm and a polydispersity index = 0.326 ± 0.02. Solid-state characterization and microscopical analysis, including polarized light, scanning, and transmission electron microscopy of SOL-based NPs, indicated the predominance of the amorphous structure of NPs with no crystals formation. The chemical integrity and stability of the spiro-structured UGF under the high voltage conditions were confirmed by 1H NMR studies on UGF/SOL NPs. The electrosprayed UGF/SOL NPs demonstrated an enhanced wettability and a 6.16-fold increase in the in-vitro dissolution compared to raw UGF. The study provides the significant impact of the electrospraying technique on the dissolution of ASDs of poorly water-soluble drugs.