The fluorescence of carbon quantum dots (CQDs) has been paid a lot of attention, but its photothermal performance attracts less attention since preparing CQDs with high photothermal conversion efficiency (PCE) is a big challenge. In this work, CQDs with an average size of 2.3 nm and a PCE of up to 59.4% under 650 nm laser irradiation were synthesized by a simple one-pot microwave-assisted solvothermal method using citric acid (CA) and urea (UR) as the precursors and N,N-dimethylformamide as the solvent under an optimized condition (CA/UR = 1/7, 150 °C, and 1 h). The as-prepared CQDs were demonstrated to have unique surface chemical states; i.e., abundant pyrrole, amide, carboxyl, and hydroxyl groups were found on the surfaces of CQDs, which ensure a high PCE. These CQDs were introduced into a thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) to form a CQDs@PNIPAM nanocomposite, and then, a bilayer hydrogel composed of CQDs@PNIPAM and polyacrylamide (PAM) was fabricated. The bilayer hydrogel can be reversibly deformed just by a light switching on/off operation. Based on the excellent photothermal performance, the developed CQDs are expected to be used in photothermal therapy, photoacoustic imaging, and other biomedical fields, and the CQDs@PNIPAM hydrogel nanocomposite is promising to be applied in intelligent device systems as a light-driven smart flexible material.