The electrochemical oxidation of 1-(phenylsulfonyl)pyrrole (1), 3-t-butyl-1-(phenylsulfonyl)pyrrole (2), 3-t-butylpyrrole (3), and 1-(tris-(isopropyl)silyl)pyrrole (4) was investigated by fast-scan cyclic voltammetry and double potential step chronoamperometry. The electron transfer rate constants were obtained and the lifetimes of the radical-cations resulting from oxidation of (1-4) were estimated using the results of the double potential step experiments in conjunction with simulation techniques. All of the radical-cations have lifetimes less than 1 ms.