Antibiotics pollutants are arousing seriously environmental issues, so the highly efficient photo-Fenton catalysts have been developed in their treatments. In this work, according to the results of XRD, Raman, FTIR, and XPS, ferrihydrite/polyaniline (Fh/PANI) catalyst could be successfully prepared in waste iron-bacterial cultures (shorted as Fe(III)/EPS-solutions) with PANI conductor ((C6H7N)n, 200–300 nm). The Fh/PANI was an optimal photo-Fenton catalyst with good physical properties for tetracycline hydrochloride (TCH, C22H25ClN2O8) degradation. In photo-Fenton systems with 30 mmol/L H2O2, 40 mg/L TCH, 0.2 g/L catalyst, and pH 4.0 under the visible light irradiation, degradation efficiency was 94% for Fh/PANI (82% for Fh). Kinetics data of TCH degradation well followed to pseudo-first-order model (R2=0.974 for Fh/PANI, and R2=0.929 for Fh). The Fh/PANI catalyst had a good stability for TCH degradation, and the efficiencies ranged in 94%−77% within its five runs. The TCH could be efficiently mineralized into H2O and CO2 inorganic molecules, and the producing ∙O2− was the key action group. These results indicate Fh/PANI photo-Fenton catalyst will have a potential application in treating antibiotic polluted waters. It also can provide a good approach of preparing Fe-(oxyhydr)oxide/conductor composites in waste iron-bacterial cultures.