We report here a kinetic study on the thermal equilibrium process between the biradical form and the quinoidal form starting from the singlet biradical form alone. A photochromic phenoxyl-imidazolyl radical complex repeatedly generates biradical species upon UV light irradiation, and the following thermal equilibrium process responsible for valence isomerization from the open-shell singlet biradical to the closed-shell quinoidal form is observed in the microsecond time region. The thermodynamic parameters for the equilibrium process were determined for the first time by nanosecond laser flash photolysis. We also found that visible-light excitation to the equilibrium state causes valence photoisomerization from the quinoidal to the biradical form, which returns thermally to the quinoidal form.