Volatile organic compounds (VOCs), which emerge as multicomponent pollutants through many industrial processes, pose a serious threat to human health and the eco-environment due to their volatility, toxicity and dispersion. Hence, the study of competitive adsorption of multicomponent VOCs is of practical and scientific importance. Herein, the perlite-supported Fe3O4@SiO2@8-hydroxyquinoline-5-sulfonic acid (perlite-Fe3O4@SiO2@8-HQ-5-SA) was designed as a novel magnetic nanoadsorbent by a simple strategy and employed for the competitive adsorption of multicomponent toluene, ethylbenzene and xylene in the vapor-phase targeted as VOCs. The successfully prepared perlite-Fe3O4@SiO2@8-HQ-5-SA was characterized by means of SEM, EDX, FT-IR, VSM and BET analyses. Adsorption capacities of 558 mg/g, 680 mg/g and 716 mg/g were achieved for single component toluene, ethylbenzene and xylene, respectively. It was concluded that the adsorption capacities for both binary and ternary components were significantly decreased compared to single component adsorption. The competitive adsorption capacity order of the binary and ternary component VOCs was xylene > ethylbenzene > toluene due to their competitive dominance. The rate-limiting kinetic analysis indicated that the adsorption rates were determined by both the film diffusion and intraparticle diffusion. The analysis of the error metrics demonstrated that the three-parameter isotherm models better described the adsorption data compared to the two-parameter models. In particular, the Toth model provided the closest fit to the experimental equilibrium data. The thermodynamic analysis indicated the spontaneous nature and probability (ΔG° <0), exothermic (ΔH° <0), physical (ΔH° <20 kJ/mol) and a declination in the degree of randomness (ΔS° <0) of the adsorption processes. The reuse efficiency of perlite-Fe3O4@SiO2@8-HQ-5-SA for toluene, ethylbenzene and xylene decreased to only by 88.91%, 88.07% and 87.16% after five recycles. The perlite-Fe3O4@SiO2@8-HQ-5-SA has a significant adsorptive potential compared to other adsorbents reported in the literature, thus it could be recommended as a promising nanoadsorbent for VOCs in industrial processes.