In this study, the effects of the catalysis of heavy metals on the pyrolysis of waste polyester textiles (WPTs) and the adsorption behaviors of the pyrolysis products of WPTs for Cr(VI) were explored. TG−DTG analysis indicated that the metal ions catalyzed the pyrolysis process by reducing the temperature of the decomposition of WPTs. The surface morphology and pore structure of the carbons were analyzed using SEM and BET. The results demonstrated that Zn−AC possessed the largest specific surface area of 847.87 m2/g. The abundant acidic functional groups on the surface of the activated carbons were proved to be involved in the Cr(VI) adsorption process via FTIR analysis. Cr(VI) adsorption experiments indicated that the adsorption process was more favorable at low pH conditions, and the maximum adsorption capacities of Zn−AC, Fe−AC, and Cu−AC for Cr(VI) were 199.07, 136.25, and 84.47 mg/g, respectively. The FTIR and XPS analyses of the carbons after Cr(VI) adsorption, combined with the adsorption kinetics and isotherm simulations, demonstrated that the adsorption mechanism includes pore filling, an electrostatic effect, a reduction reaction, and complexation. This study showed that metal salts catalyze the pyrolysis processes of WPTs, and the activated carbons derived from waste polyester textiles are promising adsorbents for Cr(VI) removal.