This work focuses on the fundamental studies of heterogeneous adsorption characteristics of mesoporous adsorbent. MCM-48 was synthesized to investigate the adsorption properties of eight different volatile organic compounds (benzene, cyclohexane, n-hexane, toluene, methanol, acetone, methyl ethyl ketone (MEK), and trichloroethylene (TCE)). The gravimetric method was used to measure the adsorption equilibrium amount. Several simple and reliable methods such as isosteric enthalpy of adsorption, thermodynamic properties, condensation pressure, organophilicity, and adsorption energy distribution were evaluated to understand the surface heterogeneity of the VOCs+MCM-48 adsorption system. This work shows that the unique features of the VOCs+MCM-48 adsorption system are highly dependent on the adsorption step, ionization potential, and Debye dipole moment of VOCs.W. G. Shim and J. W. Lee contributed equally to this work.