Using light-polarization-dependent angle-resolved photoemission, the metal-organic molecule bis(4-cyano-2,2,6,6-tetramethyl-3,5-heptanedionato)copper(II) (or Cu(CNdpm) 2 , i.e., C 24 H 36 N 2 O 4 Cu, Cu(II)) is observed to adopt a preferential orientation that depends on the film thickness and substrate when adsorbed on Co(111) and Cu(111). In addition, the final-state binding energies change with film thickness, suggesting the substrates affect the screening or charging in the photoemission final state. For Cu(CNdpm) 2 deposited on Co(111), the induced spin polarization was found to depend strongly on the molecular orbital contributions.