The high performance of Vectran^® fiber makes its application as an envelope material for airship feasible. The ultraviolet (UV) resistance of this fiber, however, is poor, and UV irradiation in the stratospheric environment causes rapid fiber aging. To protect Vectran^® fibers from UV irradiation, we prepared TiO₂ nanosols via a sol–gel method and added benzotriazole UV-1130, triazine Tinuvin^® 477, and hindered amine Tinuvin^® 123 to them to form organic/inorganic hybrid coatings. Fiber specimens were subjected to accelerated aging using a xenon arc weatherometer. Mechanical measurements as well as surface morphology and chemical composition analyses were performed to evaluate the UV-protective performance of different coatings. Hybrid coatings performed better than TiO₂ coatings in protecting fibers from UV. Among the hybrid coatings obtained, UV-1130 especially reinforced the UV-protective ability of the TiO₂ coating because of its strong UV absorbance. Although the performances of Tinuvin^® 477 and Tinuvin^® 123 were below optimal when combined with TiO₂ alone, both hybrids exhibited excellent synergistic effects when used together with UV-1130 and improved the UV-protective ability of the resultant hybrid coatings.