The interaction of benzene with polycrystalline Ag and amorphous solid water (D(2)O) deposited thereupon at 124 K was investigated. Metastable impact electron spectroscopy, Reflection-absorption infrared spectroscopy, and temperature programmed desorption were utilized to obtain information on the electronic structure and the relative contribution to the bonding properties of the aromatic molecules among themselves and with D(2)O. On Ag, the benzene molecular plane is oriented parallel to the surface in the first layer. The second layer is tilted with respect to the first one. A total work function decrease of 0.8 eV takes place during the buildup of the first two layers. On amorphous solid water, the orientational distribution of the benzene molecular planes is initially peaked at an angle parallel to the water surface. During the completion of the first adlayer a coverage-induced reorientation takes place, inducing a tilt of the benzene molecules of the first adlayer. Still larger benzene exposures appear to lead to the formation of three-dimensional benzene clusters. Films produced by codepositing benzene and D(2)O or by postdepositing D(2)O layers on benzene films display "volcano like" benzene desorption during ice crystallization.