The notion of biomass valorization has been widely adopted to alleviate low-carbon-emission anxieties with the attributes in energy-environmental sustainability via groping multiscale-structured composite, yet still suffering from the dilemma of lignin upcycling. In this context, we propose a novel dot-sheet-assembled heterostructure featuring all lignin-derived bifunctional carbon composites (Co-N-C@CDs) that includes porous Co, N co-modified nanosheets and solvent-extracted carbon quantum dots. The photo-physical properties of lignin-based CDs are refined into multicolor green- and red-emissive fractions (GCDs and RCDs) via a facile biphasic fractionation. Owing to the high-graphite and conductivity, the red-emitting RCDs are installed with lamellar Co-N-C to favor the enlarged interlayer spacing, fast ionic intercalation-transfer and reversible chemical adsorption, thereby resulting in high-performance capacitive deionization (CDI) and zinc-ion hybrid capacitors (ZIHCs). While assembling the CDI device, the Co-N-C@CDs possess a maximum adsorption capacity of 33.64 mg g−1 NaCl in water desalination with stable restorable behavior. As the cathode of ZIHCs, it delivers an operating voltage of 2.0 V and superior energy density of 209.72 Wh kg−1, posing a long-term cycling durability at high current rates. Detailed hierarchical structure readily enables the large specific surface area, excellent percolating porosity, intercalated hydrogen bonds and redox active sites, which are conducive to not only expedite ionic infiltration and charge reaction kinetics but also reduce the energy barriers of aqueous ion adsorption. The multiscale 0D-2D supramolecular assembly breaks the frontier of lignin valorization to connecting energy-environment functions, thereby meeting the needs of carbon–neutral society.