An all-optical, near-resonant laser atom trap is used to prepare an electronically excited and polarized gas target at mK-temperature for complete photo-ionization studies. As a proof-of-principal experiment, lithium atoms in the 22P3/2(mℓ = +1) state are ionized by a 266 nm laser source, and emitted electrons and Li+ ions are momentum analyzed in a COLTRIMS spectrometer. The excellent resolution achieved in the present experiment allows not only to extract the relative phase and amplitude of all partial waves contributing to the final state, it also enables to characterize the experiment regarding target and spectrometer properties. Photo-electron angular distributions are measured for five different laser polarizations and described in a one-electron approximation with excellent agreement.