Silicon oxycarbide (SiCO) ceramics obtained from polymer pyrolysis and with varied carbon contents were prepared and evaluated as new electrodic materials for sensing of tert butylhydroquinone (TBHQ) and butylated hydroxyanisole (BHA) antioxidants. Three polymers were synthesized varying molecular architecture and aromatic carbon groups, followed by pyrolysis at 1000 and 1500 °C to obtain SiCO ceramics. Graphitization and crystallization processes were evidenced, in different extent, according to precursor chemistry. SiCO at 1500 °C with intermediary carbon content provided slight improvement in the peak anodic separation of TBHQ and BHA and higher peak current compared with glassy carbon electrode (GCE). Higher acidic sites concentration together with more ordered residual carbon phase produced in situ contributed to great electrochemical performance of SiCO towards phenolic compounds detection. Therefore, the ceramic herein prepared exhibits highly efficient features as a new SiCO composited electrode for simultaneous determination of antioxidant phenolic compounds bearing in mind further analytical applications.