The conformational changes of quinoxaline-bridged cavitands deposited as Langmuir films were monitored at different pH values of the subphase using surface second harmonic generation during the compression of the monolayer at the water surface. A quantitative analysis of the susceptibility tensor elements was performed for methylene (MeCav)- and quinoxaline (QxCav)-bridged cavitands for pH values varying between 5.7 and 0.1. For MeCav (reference compound), no significant changes were observed for different pHs, confirming that the cavity does not undergo protonation or a drastic conformational change. For the QxCav, however, the results suggest a partial opening of the cavity on the basis of analysis of the compression curves.