Titania-doped chromium oxide (CTO) can serve as an active gas-sensing material. It has been successful in commercial gas sensors due to its good gas-sensing performance and stability in humid environment; especially with respect of volatile organic compounds (VOCs). CTO fibers with reticular structure were prepared by electrospinning technology and the sensing behavior upon exposure to ethanol was characterized in this report. The gas sensors made of CTO fibers show a good response to ethanol and stability for a long term at operating temperature of 400 degrees C. The experimental results have been analyzed and simulated using the response equations. The humidity effects on the sensor performance were also evaluated. The results indicate that the CTO fibers could be used in practical applications.