Solution-phase photoinduced low-spin to high-spin conversion in the Fe-II polypyridyl complex [Fe(tren(py)(3))](2+) (where tren(py)3 is tris(2-pyridylmethyliminoethyl)amine) has been studied via picosecond soft X-ray spectroscopy. Following (1)A(1) -> (MLCT)-M-1 (metal-to-ligand charge transfer) excitation at 560 nm, changes in the iron L-2- and L-3-edges were observed concomitant with formation of the transient high-spin T-5(2) state. Charge-transfer multiplet calculations coupled with data acquired on low-spin and high-spin model complexes revealed a reduction in ligand field splitting of similar to 1 eV in the high-spin state relative to the singlet ground state. A significant reduction in orbital overlap between the central Fe-3d and the ligand N-2p orbitals was directly observed, consistent with the expected ca. 0.2 angstrom increase in Fe-N bond length upon formation of the high-spin state. The overall occupancy of the Fe-3d orbitals remains constant upon spin crossover, suggesting that the reduction in a-donation is compensated by significant attenuation of pi-back-bonding in the metal ligand interactions. These results demonstrate the feasibility and unique potential of time-resolved soft X-ray absorption spectroscopy to study ultrafast reactions in the liquid phase by directly probing the valence orbitals of first-row metals as well as lighter elements during the course of photochemical transformations.