Despite the high structural symmetry of cofactor arrangement and protein environment, light-induced electron transfer in photosynthetic reaction centers (RCs) of the purple bacterium Rhodobacter sphaeroides runs selectively over one of the two branches of cofactors. The origin of this functional symmetry break has been debated for several decades. Recently, a crucial role of the substituents has been proposed by theoretical studies [Yamasaki, H.; Takano, Y.; Nakamura, H. J. Phys. Chem. B 2008, 112, 13923-13933]. Photo-CIDNP (photochemically induced dynamic nuclear polarization) MAS (magic angle spinning) NMR demonstrates that indeed the peripheral atoms show opposite electronic effects on both sides of the special pair. While the aromatic system of P-L receives electron density from its periphery, the electron density of the aromatic ring of P-M is decreased.