The use of insoluble electrodes in electrolytic oxidation for the removal of non-biodegradable organic matter, color, odor, and ammonia nitrogen from wastewater has recently received significant research attention. When employing electrochemical oxidation as a water treatment process, considering the water treatment characteristics of the electrodes and scale formation is important for efficient operation. Therefore, in this paper, the treatment characteristics and scale formation properties of an electrochemical oxidation approach that uses insoluble electrodes for the tertiary treatment of paper mill wastewater were analyzed. In particular, the effects of the operational conditions on the treatment efficiency and the occurrence of scaling were investigated. Electrolytic oxidation experiments using secondary treated pulp and paper wastewater demonstrated that it is possible to achieve a removal efficiency of 43.9% for TOC, 46.4% for TCODMn, and 89.9% for color. During the batch operation period of four weeks, an analysis of the scaling components formed on the electrodes revealed substances that resembled cement and putty in their composition. Furthermore, it was observed that scale removal from the electrodes was insufficient solely using the cross-operation of normal and reverse power supply.