Unlike the hot-melting processing of thermoplastic plastics, the processing of starch-based material relies on the addition of solvents, resulting in their low productivity, hindering large-scale industrialized production. A strategy to realize the high production efficiency of starch-based material, an environmentally friendly modification process without waste liquid generation, was designed to prepare a hot-melting starch (HMS) that can be repeatedly hot melted. Ball milling, enzymatic digestion, and deep eutectic solvent (DES) plasticization modification were combined to prepare the HMS. Ball milling destroyed the starch’s particles and the crystallinity, exposing the hydroxyl group, which allowed amylase to achieve enzymatic hydrolysis more easily. After enzymatic hydrolysis, the molecular chains of modified starch were shortened and the entanglement of molecular chains was reduced, which promoted the slip of molecular chains. The plasticization of DES, which promoted by the broken starch particles and the destroyed crystal structure, formed stronger hydrogen bonds and facilitated hot melting. Furthermore, due to the excellent hot-melting properties, HMS can be combined with sisal fiber and polycaprolactone (PCL) under solvent-free conditions. The tensile strength of HMS/sisal fiber/PCL was increased by 109%; meanwhile, the water contact angle was stabilized at 104°, when the blending ratio of hot-melting starch was 67.5% compared with HMS.