Understanding and controlling the transient optical anisotropy of strong correlation systems is of great interest in the quest for information processing and storage. Here, we report on ultrafast optical pump-probe measurements with linearly and circularly polarized laser pulses in the manganite La0.67Ca0.33MnO3 thin film. We show both the time-resolved reflectivity and the polarization state (Kerr rotation and ellipticity) of the probe-pulse at different temperatures, which are analyzed by the ultrafast intersite transition between Mn3+ and Mn4+ sites at photon energies around 1.55 eV. During the temperature-induced dynamical spectral weight transfer, a spin-flip photo-transition between spin up eg states of Mn3+ and spin down eg states of Mn4+ ions occurs and is imprinted on the optical anisotropy of the probe beam.