A model for the initial stages of anodic CdS film deposition in pH 14 sulfide solutions is presented. Cyclic voltammetry carried out over a range of sulfide concentrations consistently reveals three anodic peaks. The first peak has been found to represent the activation-controlled deposition of one-half of a CdS monolayer. This is substantiated by a computer-simulation of the current/potential curves based on a two-electron transfer mechanism. The Cd and S ions are then considered to place-exchange, and a second one-half monolayer of CdS is deposited in the second anodic peak. The third anodic peak depicts the completion of the place exchange of the film deposited in the second peak, and the deposition of one further complete CdS layer. This model is consistent with the measured charge densities and the dependence of anodic and cathodic current densities and potentials on the potential sweep rate. Also, the film structure developed according to this model of film initiation is consistent with the known crystal structure of bulk CdS.