The NiNiO/GR‐TiO2 magnetic hollow rod composites based on lignocellulose was prepared via electroless Ni and sol‐gel method to effectively solve that the composites were difficult to recycle and reuse. Rapid degradation of organic dyes was conducted. The element distribution, surface morphology, and functional groups were characterized via SEM, TEM, LSCM and FT‐IR, respectively. The structure was characterized by XRD and XPS. The photocatalytic properties were tested via TU‐1950 UV spectrophotometer. The EDS demonstrated the increase of S and N elements and FT‐IR results, indicating that methylene blue has been degraded by ring‐opening reaction. The results showed that the surface elements of the hollow rod structure were evenly distributed. The composite catalytic efficiency could reached 57.65 % and catalytic material prepared in vacuum was 93.34 % when the dosage of graphene was 50 mg. The composite materials photocatalytic system with addition of 20 mL EDTA could greatly improve the catalytic efficiency, which was up to 97.43 %.