The molecular solid [(FeL2)-L-[[](ClO4)(2)center dot CH3CN where L is 2,6-bis(3,5-dimethylpyrazol-l-ylmethyl)pyridine provides a stable high-spin (HS) state at low temperature. Photoexcitation and subsequent relaxation have been studied using light-induced excited state spin trapping [LIESST(H -> L)] in the 700-850 nm range, determination of T-LIESST, relaxation curves at different temperatures, and temperature dependence of the light-induced spin equilibrium under constant irradiation. The measured photoinduced population of the metastable low-spin (LS) state (< 30%) was drastically limited by the concomitant L -> H photoprocess. The absence of static light-induced thermal hysteresis and the stretched exponential shape of the relaxation curves respectively revealed the absence of sizable interactions and a large spreading of the activation energies attributed to the ligand flexibility. The whole data set has been simulated using a linear rate equation, with a simplified correction for the bulk extinction of light in the powder sample.