Coal-bed gas well production is too low to realize a highly efficient exploitation of the #8 coal seam in the Shanxi formation in the Nalin region. Based on the reservoir characteristics, the designed poly-aromatic-grafted silicon-quantum-dot-based desorption agent (PQS) has been developed. Then, the adsorption/desorption behavior of CBM on the coal surface under the influence of this active chemical has been studied, and the synergy effect with an anionic–nonionic surfactant to desorption of CBM has also been discussed. The results show that the developed poly-aromatic-grafted silicon quantum dot, with a median size of 4.9 nm and +5.6 mV of zeta potential in neutral condition, has a significant emission peak with 470 nm at the excitation of 380 nm and 150,000 mg/L of salinity resistance, which also generates a strong adsorption capacity on the coal surface. A promoting effect to desorption of CBM for PQS nanofluid is exhibited and the Langmuir pressure is obviously increased. However, when the PQS nanofluid is synergized with an anionic–nonionic surfactant, the desorption of CBM is further improved and the wettability of the coal surface is altered from 78.2° to 84.2°. The desorption rate for this compound system reached 65.3%. It can be found that combining the quantum size, π–π stacking, π–π conjugation, and the synergy effect between PQS nanofluid and surfactant fluid with the traditional intermolecular force has a stronger capacity for promoting desorption of CBM than the conventional desorption agent. This study provides guidance for the molecular design of the desorption agent for deep coal rock and the application of silicon quantum dots.