The nature of excess electrons has been studied in donor−acceptor (D−A) compounds based on substituted triarylamines and a nitrile-functionalized fluorene by changing the substituents on the triarylamines and also the solvent polarity. We observed that both electron push−pull capability at the distant location in the amine donor unit and solvation in solvents of varying polarity significantly affect the nitrile ν(CN) vibrations of the fluorene acceptor unit in radical anions of these D−A compounds. Quantum calculations show that the push−pull capability translates the position of an excess electron while keeping its width relatively constant. On the other hand, solvation changes both, making an electron more compact in polar media. The current study points to the idea that solvation plays a more significant role in controlling the nature of excess electrons, while synthetic modification that influences electron push−pull capability enables further tuning.