New high-yielding methods for two [RuNO(NH3)3Cl2]Cl complexes are suggested. First, the ammine ligands are arranged facially through the reaction of a concentrated ammonia solution with the ruthenium–hexanitro complex. In the next step, the treatment of the previously unknown fac-Na[Ru(NO2)3(NH3)3]·3H2O with hydrochloric acid leads to the nitrosyl complex. The mer-[RuNO(NH3)3Cl2]Cl·H2O complex is formed from the corresponding aqua complex under reflux in 6 m HCl. The complexes were studied by various methods [FTIR spectroscopy, 14N NMR spectroscopy, extended X-ray absorption fine structure (EXAFS), thermogravimetric analysis (TGA), and X-ray diffraction studies]. Metastable states (Ru–O–N) were observed in mer-[RuNO(NH3)3Cl(H2O)]Cl2, mer-[RuNO(NH3)3Cl2]Cl·H2O, and fac-[RuNO(NH3)3Cl2]Cl under illumination at λ = 443 nm at liquid-nitrogen temperatures.