Photoreaction path for the monocyanochromium (Ⅲ) ion was inferred from the experimentally observed product ratio and theoretical analysis. The angular overlap model was used to analyze the d-orbital of various intermediates along a selected reaction coordinate and to determine quartet state energy level. A loss of equatorial ammine leads to pentacoordinated square pyramid with CN- ligand in an equatorial position. The SP(CNeq) intermediate undergoes a rearrangement by the N-Cr-CN bending. This process leads to a trigonal bipyramidal intermediate in which the CN- ligand is located in equatorial position. The subsequent association with a solvent molecule should probably proceed by lateral attack an one edge of the equatorial triangle. The assumption adopted above was consistent with experimental results.