La1−xCaxVO3 composition-spread film library was fabricated by combinatorial pulsed laser deposition and their thermoelectric properties were evaluated paralelly by the multi-channel probes of Seebeck coefficient and electric conductivity. Concurrent X-ray analysis verified the formation of solid soluted films in the full composition range (0leqqxleqq1) as judged from the linear variation of the lattice constants. The Seebeck coefficients of La1−xCaxVO3 changed from a large negative value to almost zero with the increase of x, due presumably to the variation of valence in vanadium ions.The power factor in this library was as high as 0.6 μW/cm K2, which was obtained at x=0, i.e. pure LaVO3 grown at 800 °C.