BiOX (X = Cl, Br and I) and BiOX/TiO₂ photocatalysts were prepared by a facile hydrothermal approach. The BiOX/TiO₂ heterojunctions demonstrated significantly enhanced efficiency for photocatalytic decomposition of perfluorooctanoic acid (PFOA) compared with sole BiOX or TiO₂. PFOA (10 mg L¹) was completely degraded by BiOCl(Br)/TiO₂ in 8 h. Moreover, BiOCl/TiO₂ attained deep decomposition of PFOA with a high defluorination ratio of 82%. The p-n heterojunctions between BiOX and TiO₂ were confirmed by a series of characterizations. The photo-induced holes would migrate from the valance band (VB) of TiO₂ to BiOX, driven by the built-in electric field (BIEF) near the interfaces of p-n heterojunctions, the inner electric fields (IEF) in BiOX and the higher VB position of BiOX. The X-ray diffraction (XRD) and TEM characterizations indicated that TiO₂ combined with BiOX along the [110] facet, which facilitated photo-induced electron transfer in the [001] direction, thus benefiting PFOA decomposition.