The desorption performances of naphthalene and pyrene on mesoporous MCM-41, SBA-15, and CMK-3 sorbents are studied on the basis of temperature-programmed desorption experiments over the temperature range of 350-800 K at different heating rates. The kinetic parameters for each sorbate-sorbent pair are determined with combined model-fitting methods. The data for naphthalene and pyrene are best fitted with the same kinetic models on MCM-41 (with 1D mesopore channels), in contrast to those on SBA-15 and CMK-3, which have micropore-mesopore structures, leading to different desorption mechanisms for these two sorbates. SBA-15 with interconnectivity between adjacent mesopores not only shows high sorption capacities but also offers diffusion advantages in desorption, which contributes to the order of the degree of ease in desorption: SBA-15 > MCM-41 > CMK-3. CMK-3, with higher microporosity and hydrophobicity, shows stronger binding with the adsorbates while still benefiting in pyrene desorption from the consecutive mesoporosity.