Quinoxaline cavitands (QxCav) are transferred by Langmuir-Schaefer method on self-assembled monolayers (SAMs) of octadecyltrichlorosilane (OTS) and N,N-dimethyl-N-octadecyl-3-aminopropyltrimethoxysilyl chloride (DMOAP) on fused silica substrates. The molecular architectures of both the hydrophobic SAMs templates and the hybrid cavitand-organosilanes bilayers at the solid-air interface are investigated and correlated by sum-frequency vibrational spectroscopy. The results show that QxCav are always in the closed vase configuration and orient with their principal axis normal to the substrates. The role of the alkyl chains density in the SAM templates on the QxCav transfer ratio is pointed out.