We have incorporated microspheres, from 50 to 80 μm in diameter, of periodic mesoporous organosilica (inner surfaces up to 1,000 m2/g and pore sizes in the nanometre range) with two types of organic functionalities (benzene and ethane bridges, respectively) inside microstructured channels (each 200 μm wide and 100 μm deep) and, exemplarily, monitored by Raman microscopy (Raman spectroscopy through microscope optics) that the temperature characteristics of the adsorption–desorption equilibria of benzene and ethanol vary significantly with the type of organic functionality of the microspheres and the pore morphology. The integration of this class of nanostructured material into devices by means of microchannels is a promising novel approach to, among others, substance separation in analytics, micro process engineering, and micro chemistry.