Abstract The investigation of photo‐induced effects is profoundly influenced by the characteristics of photo‐excitation sources. In this study, we present a comprehensive analysis of the structures of two photoinduced linkage isomers (PLI) in a ruthenium nitrosyl complex, trans‐[Ru(py) 4 F(NO)](ClO 4 ) 2 , following irradiation with both pulsed and continuous wave (CW) light sources under low temperature conditions. The X‐ray (photo)diffraction analysis shows that the resulting PLI generated from the two types of irradiation sources, an isonitrosyl configuration of the nitrosyl ligand in the so‐called metastable state MS1, and a side‐on configuration of the nitrosyl ligand in the metastable state MS2, are identical. In‐situ optical absorption spectroscopy was employed during CW and pulsed irradiation, enabling the monitoring of the population process of these PLI. The results obtained from the infrared spectroscopic analysis after pulsed irradiation give insight into the population mechanism illustrating that the generation of the isonitrosyl MS1 occurs through a two‐step process, via the second PLI, the side‐on configuration MS2.