We report the construction of Fe(CN)63--doped copper-trimesic acid metal–organic framework (HCF/Copper-TMA). The characterization results confirmed the successful doping of Fe(CN)63- in the pores and voids of Copper-TMA. Factors affecting the doping, including the concentration of HCF, temperature, and time were optimized. The HCF-modified sensor (CPE/HCF-Copper-TMA) presents extraordinary electrocatalytic activity toward ultra-trace amounts of bisphenol A. Electrochemical tests verify that incorporation of HCF ions in the pores and voids of Copper-TMA MOF increases the sensitivity of the sensor toward ultra-trace amounts of BPA. The proposed sensor shows high sensitivity (0.923 µAµM−1) and wide linear range (linear responses in the concentration range of 0.05 – 60 μM with a detection limit of 20 nM (S/N = 3). This sensor presents advantages, including outstanding sensitivity, excellent selectivity, low detection limit, good reproducibility, and excellent stability. Moreover, the recovery values (between 96% and 106%) show that the modified sensor is a good candidate for detection of BPA residues in drinking water, milk, and orange juice samples.