An activated carbon pore-expanding technique was achieved through innovative reactivation by CO2/microwave. The original and modified activated carbons were characterized by nitrogen adsorption-desorption, scanning electron microscopy, transmission electron microcopy, and Fourier transform infrared spectroscopy. The mesopore volume increased from 0.122 cm(3).g(-1) to 0.270 cm(3).g(-1), and a hierarchical pore structure was formed. A gradual decrease in the phenolic hydroxyl and carboxyl groups on the surface of activated carbon enhanced the surface inertia of granular activated carbon (GAC). The toluene desorption rate of themodified sample increased by 8.81% compared with that of the original GAC. Adsorption isothermfittings revealed that the Langmuir model was applicable for the original and modified activated carbons. The isosteric adsorption heat of toluene on the activated carbon decreased by approximately 50%, which endowed the modified sample with excellent stability in application. The modified samples showed an enhanced desorption performance of toluene, thereby opening a way to extend the cycle life and improve the economic performance of carbon adsorbent in practical engineering applications. (C) 2017 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.