An efficient technique using citric acid and glucose based natural deep eutectic solvent (G-C-NADES) was developed to obtain ultrahigh deamidated wheat gluten (UDWG) (deamidation degree (DD) > 90%). FTIR and 1H NMR indicated intensive hydrogen bonds (HBs) in G-C-NADES supermolecules. Quantum chemical calculations and molecular dynamic simulations demonstrated that 10 wt % diluted G-C-NADES still had a myriad of HBs. Physicochemical results showed UDWG had DD up to 92.45% after G-C-NADES deamidation, that is, 22% higher than citric-acid-DWG with a weak degree of hydrolysis (1.75%). Conformational characterization demonstrated the obvious conversion from α-helix to β-sheet via FTIR, the least amount of disulfide bonds by Raman spectra, and more exposure of tryptophan residues by fluorescence measurement for UDWG. It is proven that enhanced accessible conformation of WG reached with HBs of G-C-NADESs could contribute to the improvement on nucleophilic attack of deamidation, declaring that G-C-NADES might be a potential solvent for obtaining an ultrahigh deamidation for WG to successfully guarantee the safety of wheat gluten based cereal food regarding to lowering its allergy.