Oxygen evolution reaction (OER) electrolysis, as an important reaction involved in water splitting and rechargeable metal–air batteries, has attracted increasing attention for clean energy generation and efficient energy storage. Nickel/iron (NiFe)-based compounds have been known as active OER catalysts since the last century, and renewed interest has been witnessed in recent years on developing advanced NiFe-based materials for better activity and stability. In this review, we present the early discovery and recent progress on NiFe-based OER electrocatalysts in terms of chemical properties, synthetic methodologies and catalytic performances. The advantages and disadvantages of each class of NiFe-based compounds are summarized, including NiFe alloys, electrodeposited films and layered double hydroxide nanoplates. Some mechanistic studies of the active phase of NiFe-based compounds are introduced and discussed to give insight into the nature of active catalytic sites, which could facilitate further improving NiFe based OER electrocatalysts. Finally, some applications of NiFe- based compounds for OER are described, including the development of an electrolyzer operating with a single AAA battery with voltage below 1.5 V and high performance rechargeable Zn–air batteries.