Photophysical investigations on a series of (2,4,6)‐tris‐substituted metalloporphyrin‐fullerene conjugates revealed the effects of an electron‐rich microenvironment surrounding the electron‐donating porphyrin as a function of the metal center. On one hand, for all conjugates—water‐soluble and non‐water‐soluble—ultrafast charge separation was observed upon photoexcitation. On the other hand, when examining the charge recombination dynamics for the non‐water‐soluble conjugates it becomes obvious that the (2,4,6)‐tris‐substitution stabilizes the radical‐ion‐pair state relative to the mono‐substitution in the ortho‐, meta‐, and para‐position. The more efficient protection of the electron‐donating porphyrin from solvation is thought to be the major cause for this impact. Nevertheless, the situation is slightly different for the water‐soluble conjugates. At first glance, the radical‐ion‐pair state lifetimes are, also in the case of the (2,4,6)‐tris‐substitution, longer than for the mono‐substituted ortho‐, meta‐ and para‐conjugates. Upon closer inspection, they fail, however, to exhibit any metal dependence. Competing with the protection from solvation of the dendrons, dipole‐charge interactions impact the stabilization in the polar aqueous environment and, in turn, become the dominant force governing the electron‐transfer dynamics.