The properties of Ru-ON states were studied in cis-[RuNO(NH3)2(NO2)2OH] under illumination. The structure contains two nonequivalent complexes, and the metastable state was generated for both molecules with 19(1) and 31(1)% populations. The MS1 thermal decay occurs as a one-step process at about 240 K according to differential scanning calorimetry (DSC). For the first-order reaction, the frequency factor and activation energy for the decay process were determined as 2.0(2) × 1013 s-1 and 68.3(4) kJ mol-1, respectively. Also, the simultaneous metastable state decay observed via DSC was in agreement with IR spectroscopy.