Nanomaterials such as iron oxides and ferrites have been intensively investigated for water treatment and environmental remediation applications. In this work, hollow alpha-Fe2O3 nanofibers made of rice-like nanorods were successfully synthesized via a simple hydrothermal reaction on polyvinyl alcohol (PVA) nanofiber template followed by calcination. The crystallographic structure and the morphology of the as-prepared alpha-Fe2O3 nanofibers were characterized by X-ray diffraction, energy dispersive X-ray spectrometer, and scanning electron microscope. Batch adsorption experiments were conducted, and ultraviolet-visible spectra were recorded before and after the adsorption to investigate the dye adsorption performance. The results showed that hollow alpha-Fe2O3 fiber assembles exhibited good magnetic responsive performance, as well as efficient adsorption for methyl orange in water. This work provided a versatile strategy for further design and development of functional nanofiber-nanoparticle composites towards various applications.