Photochromic [Ru(bpy)(2)(OSO)](PF6), where bpy is 2,2'-bipyridine and OSO is 2-methylsulfinylbenzoate, was investigated by femtosecond transient absorption spectroscopy. The results show that for both S-and O-bonded isomers, a (MLCT)-M-3 state is formed on a femtosecond time scale. Also observed is the formation of multiple metal-to-ligand charge-transfer (MLCT) states, representing different conformers, prior to isomerization on the picosecond time scale. These results and others are compiled in an energy diagram depicting these results.