Herein, a “nanonetwork” modified electrode was fabricated based on multiwalled carbon nanotubes and CeO2 nanorods. Scanning electron microscopy, X-ray powder diffraction and zeta potential were employed to characterize this electrode. Multiwalled carbon nanotubes negatively charged and CeO2 nanorods positively charged form “nanonetwork” via electrostatic interaction. The performance of the CeO2 nanorods-based electrode remarkably improved due to the introduction of multiwalled carbon nanotubes. The detection of rifampicin (RIF) was used as a model system to probe this novel electrode. The results showed a significant electrocatalytic activity for the redox reaction of RIF. Differential pulse voltammetry was used to detect rifampicin, the reduction peak current of rifampicin linear with the logarithm of their concentrations in the range of 1.0 × 10−13−1.0 × 10−6 mol/L, The linear equation is ip = 6.72 + 0. 46lgc, the detect limit is 3.4 × 10−14 mol/L (S/N = 3). Additionally, the modified electrode exhibits enduring stability, excellent reproducibility, and high selectivity. This strategy can be successfully used to detect trace rifampicin in samples with satisfactory results.