AbstractIn acene‐based molecular crystals, singlet exciton fission occurs through superexchange mediated by two virtual charge‐transfer states. Hence, it is sensitive to their energies, which depend on the local environment. The crucial point is the balance between the charge–quadrupole interactions within the pair of molecules directly involved in the process and those with the surrounding crystal matrix, which are governed by local symmetry and may be influenced by breaking this symmetry. This happens, for example, in the vicinity of a vacancy or an impurity and in the latter case is complemented by polarization energy and potentially by dipolar contributions. Our model calculations indicate that the superexchange coupling is sensitive enough to these factors to enable fission to be catalyzed by judiciously designed dopant molecules. In favorable cases, dipolar dopants are expected to increase the fission rate by an order of magnitude.