Herein, a series of polyimide (PI)/titanium dioxide (TiO2) organic-inorganic flexible composite microfibers with high photocatalytic performance and good reusability were prepared by combining electrospinning technology and a hydrothermal method. Under simulated sunlight, the photocatalytic characteristics of the as-prepared PI nanofibers, TiO2 nanorods, and PI/TiO2 microfibers were evaluated with photocatalytic degradation of Rhodamine B (RhB) solution. Among the tested samples, PI/TiO2-3 mL hydrochloric acid-160 °C-14 h (PI/TiO-3-160-14) (100%) exhibited a superior photocatalytic degradation rate compared to pure PI (84.0%) and TiO2 (62.2%). The enhancement of the photocatalytic performance was attributed to the Z-scheme heterojunction mechanism. When the interface was irradiated by simulated sunlight, the band edge bending, built-in electric field, and Coulomb interaction synergistically facilitated the separation and transport of electron-hole pairs in the heterojunction. This enhanced the oxidation and reduction abilities of the valence and conduction bands of PI/TiO2. These results were adequately verified by X-ray photoelectron spectroscopy (XPS) analyses and radical trapping experiments. Additionally, PI/TiO2 microfibers also demonstrated excellent photocatalytic activity toward methylene blue (MB, 81.4%), methyl orange (MO, 95.9%), and malachite green (KG, 98.9%), underscoring the versatile applicability of PI/TiO2. Further supplementary investigations illustrated that PI/TiO2 microfibers also possess excellent photostability during our extensive recycling photocatalytic experiments.