Anion exchange membrane water electrolysis (AEMWE) offers an opportunity to use inexpensive nonprecious metal catalysts. However, pure water-fed AEMWE still faces issues of durability. Herein, we compared the stability of AEMWE under different anolytes, including KOH, pure water, and a phosphate buffer (PB) using a NiFeCo oxygen evolution reaction catalyst. Upon thoroughly characterizing several changes before/after 100 h durability tests, such as the cell performance, catalyst dissolution, catalyst morphologies, impedance of the anion exchange membrane, and catalytic layer, we speculate that the change of the local pH is the main factor causing catalyst reconstruction, which further leads to the loss of cell performance in the pure water-fed mode. By using PB to control the local pH, the morphology of the catalyst will no longer change after the durability test, and the cell performance can recover to the initial performance in pure water. These results not only indicate that the catalyst structural transformation is the main reason for the deactivation of pure water-fed AEMWE but also help find a way to achieve highly durable pure water-fed AEMWE.