Chlorine gas and sodium chlorate are two base chemicals produced through electrolysis of sodium chloride brine which find uses in many areas of industrial chemistry. Although the industrial production of these chemicals started over 100 years ago, there are still factors that limit the energy efficiencies of the processes. This review focuses on the unwanted production of oxygen gas, which decreases the charge yield by up to 5%. Understanding the factors that control the rate of oxygen production requires understanding of both chemical reactions occurring in the electrolyte, as well as surface reactions occurring on the anodes. The dominant anode material used in chlorate and chlor-alkali production is the dimensionally stable anode (DSA), Ti coated by a mixed oxide of RuO2 and TiO2. Although the selectivity for chlorine evolution on DSA is high, the fundamental reasons for this high selectivity are just now becoming elucidated. This review summarizes the research, since the early 1900s until today, concerning the selectivity between chlorine and oxygen evolution in chlorate and chlor-alkali production. It covers experimental as well as theoretical studies and highlights the relationships between process conditions, electrolyte composition, the material properties of the anode, and the selectivity for oxygen formation.