Heavy solvents absorption appears to be very attractive in recovering of volatile organic compounds (VOCs) from industrial tail gas. Their high viscosities make good dispersion required but difficult to reduce mass transfer resistance. Microencapsulation techniques provide a candidate solution. In this paper, vapor pressures for toluene + poly(dimethylsiloxane) (PDMS) mixtures were measured at temperature ranging from 273.2 K to 343.2 K. Polyacrylonitrile (PAN) hollow microspheres, prepared by orifice dispersion plus solvent extraction method, was used to immobilize PDMS. The capacity was adjusted from 2.3 g to 9.3 g PDMS/g PAN by addition of cyclohexane in PDMS during solvent impregnation. The breakthrough curves of column packed with PDMS/PAN microcapsules were determined, indicating shapes close to ideality, high absorption efficiencies and considerable absorption capacities before breakthrough. The influence of operational temperature, concentration of feed and gas feed flow rate on the absorption process were investigated as well. A mathematical model, suitable for dilute gas absorption process, was used to simulate the breakthrough curves. This model has proved to be useful to fit curves and analyze the absorption kinetics of PDMS/PAN microcapsules column. After absorption, the column can be regenerated completely by gas stripping. Enrichment of toluene was founded by increasing desorption temperature. Through absorption and desorption by turns, the stability of PDMS/PAN microcapsules column was verified. (C) 2009 Elsevier B.V. All rights reserved.