Here a-Si:H is prepared by ion bombardment-activated reactive evaporation of Si in a H2O residual gas pressure ranging from 10−9 to 10−7 Torr. The Si+ ions (2.7keV) are bombarding the substrate and the walls during evaporation. Two hydrogen incorporation mechanisms are revealed by H evolution experiments, depending on the H2O residual gas pressure during evaporation. In the first mechanism H is sputtered from the walls of the system by the ion bombardment; this mechanism contributes 10 at. % to the hydrogen content. In a second mechanism Si+ bombardment on the growing layer injects H from H2O molecules adsorbed on the film surface; at least 5 at. % H is incorporated by this process. The second mechanism has a remarkable influence on the microstructure as revealed from the electrical conductivity, electron spin resonance, and infrared transmission. Indeed, Si+ bombardment-induced injection of H changes the conductivity type from variable range hopping to an activated behavior, while the dangling bond density remains low (< 1018 cm −3). The growth of [SiH2]n bundles, observed by the resonance frequency and absorption strength of the stretch mode of the Si–H dipole, is also a consequence of the H injection mechanism. It is concluded that the properties of the a-Si:H, prepared by ion bombardment-activated reactive evaporation, are explained by a microstructure, dependent on the specific hydrogen incorporation mechanism.