This paper reports on the reusability and the optimal reuse of iron-rich sludge for an electrochemical Fenton-type process using sequencing batch mode and separation batch mode reuse models. In the sequencing batch mode, processes of electrochemical treatment, neutralization, sedimentation, and re-dissolution of iron sludge were all performed in the same reactor, whereas the neutralization and sedimentation of iron sludge in the separation batch mode was carried out in an iron recovery tank separated from the electrochemical reactor. The effects of iron speciation at different pH levels were discussed. It was found that ferric ions at a pH ≤2.5 were suitable for this electrochemical Fenton-type process where ferrous ions acted as hydroxyl radical scavengers, generating brownish deposits on the cathode at pH 3. When the sequencing batch mode was applied, the current efficiency in the Fenton-type process after the iron recovery declined due to the formation of insoluble deposits on the electrodes, which decreased at lower pH. The deposits were mainly formed during the neutralization and sedimentation steps after the electrochemical process. Fortunately, iron from the sludge could be reused for the electrochemical process when the separation batch mode was used, with 100% iron recovery and no decline in current efficiency.