The internal-electrolysis (IE) process can be used as pretreatment to improve the biodegradability of yeast wastewater. The water before and after IE pretreatment was analyzed by UV, GPC, GC-MS to determine the changes in its chemical composition. The mechanism on the improvement of biodegradability by the IE process was discussed in two aspects according to the changes of chemical composition. (i) Some reactions occurred during the IE process, such as hydrolytic reaction, cracking, and redox reaction. Thus, the cyclic structure opened and changed into chains, and the macromolecular compounds were spilt to small molecule substances. All these reactions tended to simplify the structure of molecules and increase the donating electron groups so as to improve the biodegradability. (ii) The small molecule acids and alcohols in raw water or produced by the internal electrolysis process could be removed through volatilization and electrochemical adhesion, which was conducive to the removal of COD and the improvement of biodegradability of yeast wastewater.