The central dogma in constructing organic electron acceptors is to attach electron-withdrawing groups to polycyclic aromatic hydrocarbons. Yet, the full potentials of many organic acceptors were never realized due to synthetic obstacles. By combining the Wittig−Knoevenagel benzannulation, the Pd(0)catalyzed cyanation, and nucleophilic addition/oxidation cyanation, six polynitrile Z-shaped perylene diimide were synthesized. These stable and soluble electron acceptors possess LUMO energy levels comparable with those of benchmark compounds. Electrochemical investigation reveals that each additional nitrile group reduces the LUMO energy by 0.2 eV.