Structural changes of the iron(II)-tris-bipyridine ([FeII(bpy)3]2+) complex induced by ultrashort pulse excitation and population of its short-lived (0.6 ns) quintet high spin state have been detected by picosecond x-ray absorption spectroscopy. The structural relaxation from the high spin to the low spin state was followed over the entire lifetime of the excited state. A combined analysis of the x-ray-absorption near-edge structure and extended x-ray-absorption fine structure spectroscopy features delivers an Fe-N bond elongation of 0.2 Å in the quintet state compared to the singlet ground state.