Excited state processes involving multiple electron spin centers are crucial elements for both spintronics and quantum information processing. Herein, we describe an addressable excited state mechanism for precise control of electron spin polarization. This mechanism derives from excited state magnetic exchange couplings that occur between the electron spins of a photogenerated electronhole pair and that of an organic radical. The process is initiated by absorption of a photon followed by ultrafast relaxation within the excited state spin manifold. This leads to dramatic changes in spin polarization between excited states of the same multiplicity. Moreover, this photoinitiated spin polarization process can be read spectroscopically using a magnetooptical technique that is sensitive to the excited state electron spin polarizations and allows for the evaluation of wave functions that give rise to these polarizations. This system is unique in that it requires neither intersystem crossing nor magnetic resonance techniques to create dynamic spin-polarization effects in molecules.