In our present study, we explored the intraparticle diffusion of coumarin 102 (C102) in the octadecylsilyl-functionalized (ODS) silica particle in the acetonitrile (ACN)/water and butanol (BuOH)/water systems at varying temperature (T). The enthalpy-entropy compensation plots of the distribution coefficient of C102 in the ODS silica particle found that the distribution mechanism differed between ACN and BuOH. The T-dependent intraparticle diffusion coefficient (Dintra) of C102 in single particle was determined with fluorescence microscpectroscopy using laser trapping and fluorescence recovery after photobleaching method. The obtained Dintra was analyzed based on Arrhenius plots and pore and surface diffusion model. As a result, we revealed that C102 transferred in the ODS silica particle in the ACN/water solution through only the surface diffusion, and that both pore and surface diffusions was observed in the BuOH/water solution. The reason for only surface diffusion in the ACN system was found to be due to the formation of an interfacial liquid phase. These were supported by the activation energy of Dintra and surface diffusion coefficient. Moreover, we demonstrated that the proposed system allows to evaluate the T-dependence of Dintra in single particle for the first time.