Operating conditions of a chlorine dioxide (ClO2) generator create enormous challenges for the materials of construction. During the last two decades, advanced and chlorine-free ClO2 generation technology emerged but with an increased requirement for even more resistant materials of construction. In one of the most widely used processes, ClO2 is derived from sodium chlorate, sulfuric acid and methanol. Titanium is not resistant to sulfuric acid, but in conditions of mixed acid and chlorate, titanium demonstrates excellent corrosion resistance. For older ClO2 generators, use of Grade 2 (UNS R50400) titanium was sufficient, but newer technology has increased acid concentration and temperature. Grade 12 titanium (UNS R53400) was found to be less resistant than Grade 2. Grade 7 titanium (UNS R52400) performs very well in more severe conditions with 15-20 years life expectancy. In laboratory studies, Grade 16 titanium with lower palladium content (UNS R52402), showed similar corrosion resistance, but reduced tolerance at higher acid concentrations. The newest titanium grades, 26 (UNS R52404) and 27 (UNS R52254), are likely to match Grade 7 performance, but further trials are required.