Abstract: Pulsed laser-induced ultrafast photovoltaic effects have been investigated in La0.67Ca0.33MnO3 films on tilted SrTiO3 substrates fabricated by laser molecular beam epitaxy. A picosecond (ps) photovoltaic pulse without any applied bias to the film has been observed at room temperature. The rise time and full-width at half-maximum of the photovoltaic pulse are as short as 300 and 700ps, respectively when the film has been irradiated by a laser pulse of 25ps duration and 1.064μm wavelength. The photovoltage sensitivity is as large as 0.45V/mJ, and the photocurrent sensitivity is more than 0.25A/mJ. The mechanism is proposed as the combination of a photoelectron and a Seebeck processes, and the Seebeck coefficient we obtained, ∼4.04μV/K, is one order larger than previous report. [Copyright &y& Elsevier]