3D multiporous Co, N co-doped MoO2/MoC (3D Co,N-MoO2/MoC) nanorods hybrids were successfully synthesized via carburizing core-shell ZIF-67-cladded MoO3 nanorods precursor at high temperature. As-fabricated Co,N-MoO2/MoC nanorods coated glassy carbon electrodes (GCE) was demonstrated to possess superior electrocatalytic activity for the electro-oxidation of acetaminophen (AC) and 4-aminophenol (4-AP). Such excellent electrochemical performance was largely attributed to the synergistic effect of the unique multiporous structure, the optimal component and abundant active sites of the nanorods. The corresponding electrode reaction mechanisms were studied in detail in this article. Under optimal conditions, the linear detection ranges were 0.05–200.0 μmol/L for AC and 0.05–140.0 μmol/L for 4-AP, respectively, with the low detection limits of 0.013 μmol/L and 0.012 μmol/L. Furthermore, the 3D Co,N-MoO2/MoC/GCE revealed excellent sensitivity, good reproducibility, stability and anti-interference ability. The developed electrode was evaluated towards the detecting AC and 4-AP in biological fluids, environment water and pharmaceutical formulations with satisfactory recovery, which had a broad application prospect.