The ability to modulate luminescence is crucial for organic light-emitting molecules. However, the correlation between molecular structure and emission is not always obvious and systematic. Here, using a well-established empirical rule on electrophilic substitution involving directing groups in organic chemistry, we present a model system, where two luminophores are covalently linked to benzene ortho, meta, and para to each other, to demonstrate that the rule can also be useful in predicting the fluorescence and phosphorescence behaviors of these disubstituted benzene molecules. The benzene ring works as a "molecular wire" that transduces electron density when the two luminophores form ortho- and para-isomers, while little to no transduction can be noted for the meta-isomer, based on well-established organic chemistry. We anticipate that many more "textbook examples" of electronic directing in organic chemistry can be used for systematic modulation of molecular fluorescence and room-temperature phosphorescence.