How to propel an efficient exploitation of waste streams is a pivotal tache for the long-range augment of hydrothermal biomass valorization. A facile approach was proposed to simultaneously produce carbon dots (CDs), fermentable sugar, and cellulose enzymatic lignin from agricultural straw with the aid of ionic liquid (IL, 1-aminoethyl-3-methylimidazolium nitrate, [CNHMIm][NO]) catalyzed hydrothermal treatment. The graphite N-doped CDs with bright-blue fluorescence, which was mainly derived from the incorporation of hemicellulose (e.g. xylooligosaccharides), lignin and [CNHMIm][NO], exhibited an average-diameter of 8.14 nm. The exfoliation of amorphous parts and robust fibers was formed to improve cellulose digestibility from 14.7 to 81.6%. The efficient recovery and checkup of lignin pave a way for its potential depolymerization into arenes. This protocol offers a significant benefit for large-scale hydrothermal biorefinery where reduction of process waste is a prime concern, and leads to high-value products (i.e., CDs and lignin) that also fosters the feasibility of bioethanol.