Natural hydro-low-transition-temperature mixtures (NH-LTTMs) tend to be the most favorable next-generation green solvents for biomass pretreatment, as they are cheap and environmental friendly. The amount of water bound into the NH-LTTMs greatly affected their thermal stability, whereby the highest thermal stability was (47.57 kcal mol(-1)), which indicated the highest solubility, was optimized with the molar ratio of hydrogen bond donor (HBD)-hydrogen bond acceptor (HBA)-water (2: 4: 3) at a temperature of 60 degrees C. Hydrogen bonding networks of the NH-LTTMs, which led to the dissolution of biomass, were confirmed by the alteration in the peaks of the involved bonds and resonance signal to lower field through FTIR and H-1 NMR spectra, respectively. The components evidenced in high-resolution mass spectra of extracted lignin showed its high potential to be valorized into useful fuels and chemicals.