The multi-electron redox reaction of an organic radical based composite cathode comprised of poly(2,2,6,6- tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA)-Ketjenblack is investigated using an in situ electrochemical-electron spin resonance (ESR) methodology. The experiments allow each electrochemical state to be associated with the chemical state (or environment) of the radical species upon the cell cycling. In situ ESR spectra of the composite cathode demonstrate a two-electron redox reaction of PTMA that is from an aminoxy anion (n-type, at 2.5–2.6 V vs. Li/Li+) via a radical (at 3.2–3.5 V vs. Li/Li+) to an oxoammonium cation (p-type, at 3.7–4.0 V vs. Li/Li+). In particular, an adjustable n-type doping process of PTMA is first observed during the discharging process. Moreover, two different local environments of radical species are found in the PTMA-Ketjenblack composite electrode that includes both concentrated and isolated radicals. These two types of radical species, showing similarities during the redox reaction process while behaving quite different in the non-faradic reaction of ion sorption/desorption on the electrode surface, govern the electrochemical behavior of PTMA based composite electrode.