To produce antioxidant substances from agricultural waste Camellia spp. fruit shells before their further utilization, gallic acid from five kinds of Camellia spp. fruit shells was separated on specific recognition by deep eutectic solvent molecularly imprinted polymers (DES@MIPs), which were prepared by bulk polymerization using gallic acid as the template and deep eutectic solvents (α-methylacrylic acid and choline chloride) as functional monomers. The optimized DES@MIPs were characterized by scanning electron microscopy, particle size analysis, nitrogen sorption porosimetry, elemental analysis, Fourier transform infrared spectroscopy, and thermal gravimetric analysis. The adsorptive behavior of gallic acid on DES@MIPs was also investigated. The results indicated that DES@MIPs were successfully prepared as mesoporous materials with average pore diameter of 9.65 nm and total pore volume of 0.315 cm3 g−1, and the adsorption behavior was multilayer adsorption and pseudo-second-order kinetics with the saturation adsorptive capacity of gallic acid reaching 0.7110 mmol g−1. Although the content of gallic acid in five fruit shells was quite different, the purification recovery of gallic acid was high, ranging from 87.85–96.75% with a purity over 80%. Thus, the purification of gallic acid from Camellia spp. fruit shells could be realized feasibly using DES@MIPs with favorable economic and environmental benefits.