We show that high-resolution laser spectroscopy can probe surface interactions of gas confined in nanocavities of porous materials. We report on strong line broadening and unfamiliar line shapes due to tight confinement, as well as signal enhancement due to multiple photon scattering. This new domain of laser spectroscopy constitute a challenge for the theory of collisions and spectroscopic line shapes, and open for new ways of analyzing porous materials and processes taking place therein.