The exploration of an economical and efficient noble metal-free heterogeneous catalyst is of great significance for the construction of an electrochemical method for the simultaneous detection of Dopamine (DA) and acetaminophen (AC). In this paper, we employed a facile strategy to obtain Co/Mo2C nanoparticles embedded in nitrogen-doped carbon hollow nanocages (Co/Mo2C@N-C HNCs) heterogeneous structure by pyrolyzing ZIF-8@ZIF-67 precursor. The unique hollow structure ensures a fast electron transport channel, N doping regulates the local electronic structure of the catalyst, and the synergistic effect with Mo2C and Co nanoparticles provides more electrocatalytic active sites. The Co/Mo2C@N-C HNCs electrode separates the overlapping voltammetry peaks of DA and AC into two distinct voltammetry peaks (△E=200 mV), thereby selectively determining DA in the presence of AC and vice versa. The transfer coefficient (α) and electron transfer number (n) of DA and AC electrocatalytic oxidation were also studied. Using Co/Mo2C@N-C HNCs as electrode, an electrochemical sensor platform for the simultaneous detection of acetaminophen (AC) and dopamine (DA) was first constructed with linear range of 1–185 μM, and 1–100 μM and low detection limit of 0.35 μM and 0.46 μM for AC and DA, respectively. Satisfactory results have been obtained in the determination of human serum and acetaminophen tablets samples. DFT calculation reveals the molecular mechanisms for DA and AC interacting with the Co/Mo2C@N-C HNCs catalysts. This strategy provides a new idea for the selective determination of several analytes in complex substrates.