Ammonia and amine ligands are commonly assumed to be σ-only ligands in coordination chemistry, i.e. they are not expected to interact significantly with a metal via a π path. Ligand field analyses employing the Angular Overlap Model resulted in good fits to experimental data without a π parameter for ammonia ligands, thereby supporting this assumption. In this work, we challenge this assumption and suggest that it is an oversimplification. We use complete active space calculations for electronic structure analyses of copper ammine complexes that are in good agreement with the transitions observed in experimental UV-vis spectra. These findings lead to a reinterpretation of the experimental spectra that necessitates a significant π interaction of the ammonia ligands. The strength of the ammonia π interaction is evaluated by parameterizing the ligand field splittings of a series of metal hexammine complexes ([M(NH3)6]n+ with M = Cr, Mn, Fe, Co, Ni, Ru, Os and n = 2, 3) and selected tetrammine complexes ([M(NH3)4]n+ with M = Cr, Mn, Fe, Co, Ni and n = 2 or 3) with the Angular Overlap Model. The resulting π parameters show that ammonia is a π donor of similar strength as chloride.