In this work,we report the influence of Co-doping on the electronic band structure,dielectric and magnetic properties of La0.1Bi0.9Fe1-xCoxO3 ceramics.X-ray photoelectron spectroscopy investigation shows that Co dopant can shift the valence band spectrum and core-level lines of constituent elements towards higher bind energy regions simultaneously increase the concentration of oxygen vacancies in ceramics.The effects of dopant are discussed with focus given to the Co-doping induced enhancement of electrical conductivity and resistive switching phenomena.