Heterogeneous Fenton processes with solid catalysts have gained much attention for water and wastewater treatment in recent years. In the field of solid catalysts, zero valent iron (ZVI) is among the most applicable due to its stability, activity, pollutant degradation properties and environmental friendliness. The main limitation in the use of ZVI in heterogeneous Fenton systems is due to its deactivation in neutral and alkaline conditions, and Fenton-like processes have been developed to overcome this difficulty. In this review, the effect of solution pH on the ZVI-Fenton performance is discussed. In addition, the pH trend of ZVI efficiency towards contaminants removal is also considered in oxic solutions (i.e., in the presence of dissolved O2 but without H2O2), as well as in magnetic-field assisted Fenton, sono-Fenton, photo-Fenton and microwave-Fenton processes at different pH values. The comparison of the effect of pH on ZVI performance, taking into account both heterogeneous Fenton and different Fenton-like processes, can guide future studies for developing ZVI applications in water and wastewater treatment.