TiO2/BiOI/CA electrodes with improved conductivity, reduced photoelectron-hole recombination rates, and increased reaction sites based on p-n type heterojunctions were constructed on carbon aerogels (CA) as photoelectrode substrates. Characterization based on ultraviolet-visible diffuse reflectance spectroscopy, photocurrent measurements, and impedance analysis showed that the TiO2/BiOI/CA photoelectrode with a Ti/Bi mole ratio of 0.4 exhibited the best visible light absorption, lowest photogenerated electron-hole pair recombination rate, and strongest photocatalytic degradation, with 90.4% degradation of phenol under 120 min of light. Moreover, the stability of this electrode remained at a high level. This was mainly because the energy levels of TiO2 and BiOI matched each other and the p-n heterojunction formed adjusted the energy band structure of the composite material, widened the electron transfer path, formed an internal electric field between the phase interfaces, had a higher electron transfer rate, and reduced the photogenerated electron-hole recombination rate. Since ˙OH and ˙O2- are the main active substances in the degradation of phenol, the TiO2/BiOI/CA photoelectrodes had higher degradation efficiency than BiOI/CA electrodes. This study provides a unique concept for the treatment of organic pollutant wastewater and electrode design for photoelectrocatalysis.