We demonstrate optical orientation in Ge/SiGe quantum wells and study their spin properties. The ultrafast electron transfer from the center of the Brillouin zone to its edge allows us to achieve high spin polarizations and to resolve the spin dynamics of holes and electrons. The circular polarization degree of the direct gap photoluminescence exceeds the theoretical bulk limit, yielding ∼37% and ∼85% for transitions with heavy and light holes states, respectively. The spin lifetime of holes at the top of the valence band is estimated to be ∼0.5 ps and it is governed by transitions between light and heavy hole states. Electrons at the bottom of the conduction band, on the other hand, have a spin lifetime that exceeds 5 ns below 150 K. Theoretical analysis of the spin relaxation indicates that phonon-induced intervalley scattering dictates the spin lifetime of electrons.