Redox behavior is a fundamental and fascinating feature of polycyclic aromatic hydrocarbons (PAHs). Cyclic voltammetry (CV) measurements are commonly performed to estimate the electronic structure of PAHs and to determine the stability of their oxidation and reduction states. However, the influences of electrolytes on electrochemically oxidized/reduced PAHs have rarely been discussed. In this note, we report voltammetric analyses of five PAHs (anthracene, 9,10-dimethylanthracene, phenanthrene, pyrene, and perylene) in Bu4NB(C6F5)4/CH2Cl2 and Bu4NTfO/CH2Cl2, respectively, to highlight how the electrolyte-coordination affects the oxidative voltammetric behavior of PAHs. In most cases, reversible voltammetric responses were obtained with Bu4NB(C6F5)4/CH2Cl2, suggesting that this electrolyte is enough weakly coordinating to investigate its intrinsic oxidation behavior. On the other hand, irreversible voltammetric responses were obtained with Bu4NTfO/CH2Cl2, indicating that the presence of a relatively coordinating anion, TfO−, destabilizes the radical cation species and induces further chemical and electrochemical processes. This study provides hints for rational electrolyte design to properly understand the redox behavior of molecules and maximize the potential of functional molecules for applications related to redox chemistry.