A new approach to hydrothermally synthesize nanocrystalline titanium dioxide with a rutile structure and spherulite-like morphology from titanyl citrate is described herein. It was found that titanium dioxide formed as a result of titanyl citrate thermolysis with the following products: rutile nanocrystals, itaconic acid, and carbon dioxide. Rutile nanocrystals were rod-shaped and oriented in the (101) crystallographic direction. The position of the rutile nanocrystals in the spherulites and pores between the nanocrystals lead to high electrocatalytic activity for the oxygen evolution reaction in alkaline aqueous solutions. The process is characterized by a Tafel slope of 49 mV/dec.