The ligand field photolysis of three Zra/i$-Cr(NH3)4(CN)Xz+ ions, with X = H20, NCS", and F", has been studied in acidic aqueous solution (10"3 M HC104). These complexes are electronically unusual, in that the CN" and X axial groups act in opposition on the splittings of the octahedral states and, moreover, are respectively -acceptors and -donors. In each case photoaquation of all three types of ligands is observed. For X = H20, transcis photoisomerization is taken as a measure of water photoexchange. The total quantum yields are in the 0.2-0.4 range, virtually wavelength independent. Equatorial and axial reactivities are of comparable magnitude, their ratios being 0.32, 2.5, and 3.0 for X = HzO, NCS", and F~, respectively, upon irradiation of the long-wavelength maximum. This is consistent with the small energy separation between the lowest excited quartet states, 4E and 4B2. The results are compared with the predictions of various photolysis models and are analyzed particularly in terms of excited-stateand -bonding changes. All three complexes phosphoresce from the lowest doublet state under photochemical conditions, with 20 °C lifetimes of 1.1, 30, and 0.2 gs, respectively. Luminescence and photoreaction quenching by Cr(C204)33" have been investigated in the case of Zrani-Cr(NH3)4(CN)(NCS)+. The quantum yields for the three photoaquation modes decrease in parallel with emission and, upon complete doublet quenching, one-fourth of the photoreactivity remains unquenched. The proportion in ligand labilization is the same for both the unquenchable and the quenchable photochemistry. This suggests a common precursor (4E/4B2) for all photoreactions, hence, doublet deactivation mainly via back intersystem crossing to the lowest excited quartet state(s).