A novel platform based on evanescent wave sensing in the 6.5 to 7.5 µm wavelength range is presented with the example of toluene detection in an aqueous solution. The overall sensing platform consists of a germanium-on-silicon waveguide with a functionalized mesoporous silica cladding and integrated microlenses for alignment-tolerant back-side optical interfacing with a tunable laser spectrometer. Hydrophobic functionalization of the mesoporous cladding allows enrichment of apolar analyte molecules and prevents strong interaction of water with the evanescent wave. The sensing performance was evaluated for aqueous toluene standards resulting in a limit of detection of 7 ppm. Recorded adsorption/desorption profiles followed Freundlich adsorption isotherms with rapid equilibration and resulting sensor response times of a few seconds. This indicates that continuous monitoring of contaminants in water is possible. A significant increase in LOD can be expected by likely improvements to the spectrometer noise floor which, expressed as a relative standard deviation of 100% lines, is currently in the range of 10−2A.U.