Time-resolved electron paramagnetic resonance and luminescence spectra have been observed for the lowest excited states of 1,10-phenanthroline (phen), 2-methyl-1,10-phenanthroline (2-Mephen), 2,9-dimethyl-1,10-phenanthroline (2,9-Me 2 phen), 4,7-Me 2 phen, 5,6-Me 2 phen and their Zn 2+ complexes in rigid solutions at 77 K. The sublevel preferentially populated by intersystem crossing (ISC) is the out-of-plane sublevel in Zn-2-Mephen-Cl 2 and Zn-2,9-Me 2 phen-Cl 2 . The observed anisotropy in the ISC of these Zn 2+ complexes is anomalous for the ligand-localized 3 ππ* state. The luminescence spectra and fluorescence lifetimes indicate that the increment of the ISC rate for the out-of-plane sublevel is responsible for the anomalous anisotropy in the ISC of these Zn 2+ complexes.