AbstractThe formulation of optoelectronic components into 1D nanostructures allows the promotion of new materials with multifunctionalities. In this work, it is demonstrated that new synthesis of photocatalytic carbon nanofiber decorated with semi‐embedded titanium oxide (TiO₂), namely, TiO₂@carbon fiber, is conveniently accessed through the electrospinning of polyacrylonitrile polymer and TiO₂ particle comixture, and then followed by photon‐activated self‐erosion to expose the embedded TiO₂ and carbonization. The hybrid nanofibers are characterized by field emission scanning electron microscopy, transmission electron microscopy, and X‐ray diffraction analysis. Furthermore, the photocatalytic activities of the resultant fibers are tested with photodegradation of Rhodamine B in aqueous solution, which reveals that the carbon nanofiber with semi‐embedded TiO₂ drastically improved catalytic efficiency and recyclability, comparing to those fibers without or with embedded TiO₂.