Some of the important goals in the development of the electro-Fenton (EF) process are to increase the performance of the electrodes while reducing their size as an alternative for expensive electrodes, expanding the active pH range, and also generating reactive oxygen species (ROSs) directly without using other homo/heterogeneous catalysts. This work modified graphite felt (GF) using a rapid and in-situ synthesis with Co/Zn doped mixed-metal ZIF. After calcination, various physicochemical analyses, including XRD, SEM, and XPS, confirmed that a carbonic material doped with mixed-oxide CoO/Co2O3 is embedded on the surface of GF fibers. LSV analysis showed that the modification significantly improved the electrode activity for O2 reduction. The modified CoZnCal-GF electrode showed good performance and higher kinetics in the EF process. It removed 87% of rifampin (RIF) in a short period of 30 min without any homo/heterogeneous catalysts. The selected conditions for this process were 1.0 V, 40 mg/L, and 5.6 for applied voltage, initial RIF concentration, and pH, respectively. The non-radical species 1O2 showed the most important role in removing RIF. LC-MS analysis was performed, and while confirming the complete removal of RIF, it was used to investigate the degradation pathway and identify the produced intermediates.