We report the observation of a net spin polarization in the n=1 image-potential state at the Cu(001) surface. The spin polarization is achieved by spin-selective multiphoton excitation of electrons from the spin-orbit split Cu d bands to the image-potential state using circularly polarized ultrafast light pulses. We show that by tuning the exciting photon energy, we can adjust the resonant coupling of the image-potential state to d bands of different double-group symmetry. This allows us to tune the spin polarization injected into the image-potential state.