We have investigated the photoinduced phase transition of spin crossover complex [Fe(2-picolylamine)₃]Cl₂EtOH by Raman and infrared absorption spectroscopy and clarified that the symmetry breaking, which has not appeared in the thermal equilibrium state, takes place in the photoinduced phase. In order to clarifythe origin of the symmetry breaking, the local structure around iron ion has also been studied in the photoinduced phase by x-ray absorption spectroscopy. In addition, we proposed a qualitative modeltoexplain the appearance of a new-material phase, which has not been observed in the thermal equilibrium state but could be created by the photoinduced phase transition.