Pyrolyzed photoresist carbon electrodes (PPCEs) are fabricated by the photopatterning of a negative tone epoxy-based photoresist, SU-8, through optimized standard UV photolithography. The electrochemical characteristics of PPCEs are investigated in dimethyl sulfoxide (DMSO), observing a wider accessible potential window and a smaller capacitance with respect to glassy carbon electrodes. PPCEs are used to study the cyclic voltammetric behavior of bilirubin (BR) in DMSO. Detailed information is obtained on the multiple steps involved both in the electrochemical oxidation and reduction of BR. Interesting points concerning the electrochemical oxidation of BR to biliverdin are clarified, identifying the formation of an intermediate whose fate depends on the time scale of the electrochemical experiment. PPCEs are also used to electrogenerate the superoxide anion O-2(-center dot) in DMSO for studying possible reactions between BR and O-2(-center dot). The results obtained demonstrate that BR is an efficient superoxide scavenger and that a concentration 2 mM of BR is high enough to consume all the O-2(-center dot) generated by oxygen reduction at the PPCE/DMSO interface. (C) 2014 Elsevier Ltd. All rights reserved.