In this work, we present observations of ultrafast carrier dynamics and spin polarization in a multiferroic manganite BiFe0.5Mn0.5O3 film excited by linearly and circularly polarized femtosecond pulses, respectively. The d-band charge transfer transition is reasonably assigned to Γ3 → Γ5. The transient reflectivity decay on a time scale as fast as only 0.3 ps is consistent with the picture of ultrafast electron-phonon coupling. The ultrafast switching of polarization ellipticity (< 150 fs) originates from a transient coherent spin polarization by optical orientation. The ultrafast spin polarization switching is assigned to the Raman coherence process.