The constituent phases, electrical conductivity, and Seebeck coefficient of Ca-Si films deposited on (001) Al 2 O 3 substrates by a radio frequency magnetron sputtering method using a Mg disk target with Ca and Si chips are investigated. X-ray diffraction analysis indicates that the films consist of a single phase of CaSi 2 , CaSi or Ca 5 Si 3 that are deposited together with the films consisting of a mixture of CaSi 2 and CaSi. Films with a CaSi 2 or CaSi single phase exhibit a metallic behavior. In contrast, films with a Ca 5 Si 3 single phase show p-type conduction and their Seebeck coefficient reaches 90 lV/K at 400°C.