For fabricating photovoltaic BaSi2 films with controlled carrier density and suppressed oxidation by thermal evaporation, the mechanism determining the film composition from incongruently evaporated BaSi2 must be elucidated. We investigated the effects of source premelting, substrate temperature, and thickness on the structural and electrical properties of evaporated BaSi2 films. It is found by room-temperature deposition that the vapor composition continuously changes from being Ba-rich to being Si-rich. Source premelting suppresses the deposition of Ba-rich vapor. Deposition at 600–700 °C shows that BaSi2 forms through the mutual diffusion of Ba and Si, followed by surface oxidation by residual gas. Surface oxidation can be suppressed by a-axis-oriented growth. By changing the film thickness, the optimum thickness to obtain homogeneous films with suppressed oxidation is revealed. Sufficient diffusion leads to high film resistivities and low electron densities, which demonstrates a close relationship between the film composition and the electrical properties.