Titania (TiO2) modification with carbon nanolayers to increase substrate adsorption in the vicinity of the photocatalytic sites and high migration efficiency of photoinduced electrons at the carbon/TiO2 interface lead to a photocatalyst with enhanced efficiency. Herein, surface hybridization with carbon nanolayers of continuous TiO2 nanofibers based on the electrospinning technique were fabricated. Compared with TiO2 nanofibers, the photocatalyst of carbon-layer-covered TiO2 nanofibers presented a higher photocatalytic activity under UV irradiation for the degradation of organic compounds (methylene blue). The photostability was retained after five cycles under UV irradiation.