In this study, zinc ferrate (ZnFe2O4) and polyaniline (PANI) were coated on the surface of FAC by hydrothermal and in situ polymerisation using the floating property of fly ash cenospheres (FAC) to form PANI‐ZnFe2O4/FAC composites. Compared with other reference materials, the PANI‐ZnFe2O4/FAC material not only solves the problem of less easy recycling, but also has significantly enhanced photocatalytic activity for methylene blue (MB). The significant increase in catalytic efficiency is attributed to the synergistic effect of PANI and ZnFe2O4 on the FAC surface resulting in efficient separation and low photogenerated charge complexation rates. In addition, cycling tests have shown the material to be stable and reusable. Active species capture experiments show that ⋅O2− and h+ play a dominant role in the reaction system.