This work constructed a new-type bisphenol A (BPA) electrochemical sensor on the basis of self-assembled multi-layer strategy of Ce-Zn-metal organic framework/multiwall carbon nanotube (Ce-Zn-MOF/MWCNT)–modified glassy carbon electrodes (GCE). The novel bimetallic Ce-Zn-MOF are synthesized by 1,3,5-benzenetricarboxylic acid (H3BTC) as the ligand via a hydrothermal approach. Bimetallic Ce-Zn-MOF with multiple catalytic sites and ultra-high specific surface area introduces traditional electrode modification materials, which improves the conductivity and catalytic ability of MWCNTs. Field emission scanning electron microscopy, transmission electron microscope and Powder X-ray diffraction were performed to analyze the Ce-Zn-MOF/MWCNTs. The electrochemical property was researched utilize differential pulse voltammetry (DPV), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). In the optimum conditions, the proposed sensor exhibited a wider dynamic linear range of BPA determination in 0.1 to 100 μmol·L−1 with a detection limit of 7.2 nmol·L−1 (S/N = 3). This measurement of BPA was successfully used for drinking water with desirable recovery from 96.5 to 103.4%.