In this study, a hydrothermal process was utilized to grow mixed-valence CuFe2O4/Cu0 nanosheets on carbon fiber paper, forming a three-dimensional hierarchical electrode (CuFe2O4/Cu0@CFP). The ordered array structure, coupled with the porous bowl-like structure, enhances the exposure of more electrode active sites and facilitates analyte penetration, thus enhancing the electrode sensing performance. As a binder-free sensor, the CuFe2O4/Cu0@CFP sensor exhibited remarkable sensitivity in detecting Malachite Green (MG), Sunset Yellow (SY) and Tartrazine (TA) over wide concentration ranges: 0.1–300 μM for MG (R2 = 0.994), 0.005–200 μM for SY (R2 = 0.996), and 0.005–300 μM for TA (R2 = 0.995) with low detection limits of 0.033 μM for MG, 0.0016 μM for SY, and 0.0016 μM for TA (S/N = 3), respectively. Additionally, the 3D CuFe2O4/Cu0@CFP sensor detected MG, SY, and TA in a mixed solution with satisfactory results. It also performs well in beverage, fruit juice powder, and jelly samples, with results matching those from HPLC.