In this work, β-FeOOH precursors were grown on at Al 2 O 3 ceramic matrix by a hydrothermal-assisted solgel composite method, followed by heat treatment to obtain α-Fe 2 O 3 /Al 2 O 3 photo-Fenton catalysts. The effect of heat treatment temperature on the microstructure and photo-Fenton performance of α-Fe 2 O 3 /Al 2 O 3 photo-Fenton catalysts was studied emphatically. The PANI@α-Fe 2 O 3 /Al 2 O 3 photo-Fenton composite (PFA-550) were obtained by coating polyaniline (PANI) on the optimized α-Fe 2 O 3 /Al 2 O 3 (FA-550) surface via in-situ polymerization, and subsequently used as an anode to assemble a photo-Fenton reactor for the removal of methylene blue (MB). The effect of pH value and applied electric eld on MB removal of the photo-Fenton reactor was investigated. It was shown that α-Fe 2 O 3 nanotubes was uniformly distributed over the surface of the at Al 2 O 3 ceramic in the FA-550 heated at 550°C, which exhibited high photo-Fenton activity. Compared to FA-550, PFA-550 exhibit superior photo-Fenton activity. In addition, PFA-550 have excellent photo-Fenton activity in a wide pH range (pH=3.92~9.21) rather than narrow range (pH=2.0~3.5) in conventional Fenton reaction. The migration of photogenerated electrons(e -) were promoted by external electric eld from the surface of PFA-550 to the counter electrode. The removal rate of MB was substantially increased with the effective improvement of the separation of photogenerated e --h + . Highlight β-FeOOH/Al 2 O 3 was synthesized using a hydrothermal-assisted sol-gel composite method. α-Fe 2 O 3 nanorods and nanotubes were formed by heating β-FeOOH precursors covered on Al 2 O 3 ceramic matrix. PANI@α-Fe 2 O 3 /Al 2 O 3 were obtained by coating polyaniline (PANI) on the optimized α-Fe 2 O 3 /Al 2 O 3 surface. PANI@α-Fe 2 O 3 /Al 2 O 3 photo-Fenton composite exhibited excellent photo-Fenton activity over a wide pH range.The photo-Fenton activity of PANI@α-Fe 2 O 3 /Al 2 O 3 was increased under both visible light and an applied electric eld.