Integrating single molecule measurements with bulk experiments offers a powerful approach to understand electron transport . We performed a series of bulk electrochemical and spectroscopy experiments to understand the electronic properties of PPP, focusing on the origin of the high conductance state. Results from cyclic voltammetry (CV) experiments show a distinct oxidation wave on the forward scan at approximately 0.65 V vs. Ag/AgCl, with only a small reduction peak at 0.15 V on the return scan (Figure ). The absence of a prominent return peak in the CV indicates that a distinct chemical process occurs after oxidative electron transfer. A second distinct electron transfer event was observed when the positive limit of the potential window was expanded from 0.8 V to 1.0 V, however this second electron transfer event leads to the formation of a surfacebound species (Supplementary Figure ). Bulk electrolysis was performed to identify the nature of the products generated upon electrochemical oxidation of PPP. The potential was maintained at 0.8 V during electrolysis to isolate the first electron transfer event and avoid possible film formation on the electrode surface. The solution in the working electrode compartment exhibited dramatic changes in color, changing from colorless to purple upon oxidation (Figure ). All electrochemical experiments were performed in triplicates, and the integrated charge was used to determine the total number of electrons transferred during the electrochemical oxidation. Our results (Figure ) indicate that one electron was transferred, which suggests that the electrochemical oxidation of PPP forms a radical cation species.