Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were measured in dichloromethane (DCM) with n-Bu4NPF6 as the supporting electrolyte to experimentally ascertain the HOMO and LUMO energy levels. A reversible oxidation wave (E1/2 = 0.66 V vs SCE), ascribed to the oxidation of the PXZ groups, was observed for 4PXZPh-[10]CPP from the CV, while the DPV shows a single oxidation peak at 0.67 V vs SCE (Figure ). The HOMO of 4PXZPh- [10]CPP is calculated to be -5.01 eV from the DPV, which is more destabilized than that of [10]CPP (-5.54 eV) measured in C2H2Cl4. Similar to other CPPs, no reduction wave was observed for 4PXZPh-[10]CPP within the DCM solvent window. The LUMO level for 4PXZPh-[10]CPP (-2.08 eV) was inferred from the HOMO energies and the optical gap (Eg), which itself was determined from the intersection of the normalized absorption and fluorescence spectra in toluene at 2.93 eV. The LUMO level of 4PXZPh- [10]CPP is destabilized compared to that of [10]CPP (-2.54 eV), which matches the trend observed from the DFT calculations.