Barium titanate materials displaying a positive temperature coefficient of resistivity are ubiquitously employed as thermistors in electrical current and voltage control systems, as well as in gas and thermal sensing applications. The positive temperature coefficient of resistivity effect is widely accepted to be a grain boundary-based phenomenon, although detailed studies on grain boundary structure and chemistry, and their influence on the resulting electrical properties, are seriously lacking. Tailoring of the positive temperature coefficient of resistivity electrical characteristics, for specific high-value applications, will require improved understanding and control over grain boundary phenomenon. A comprehensive overview of the development of barium titanate-based positive temperature coefficient of resistivity ceramics is initially presented. We then advance to a discussion on emerging grain boundary characterization techniques, specifically, a stereographic analysis of electron backscatter diffraction data that could assist in enhancing control over BaTiO 3 defect chemistry and microstructure, through characterization and subsequent manipulation of the population of grain boundary types. These techniques have great potential for increasing the understanding of the delicate interplay between processing conditions, chemistry, microstructure, and functional electrical properties, and are relevant to the development of advanced, high-performance ceramics and electroceramics in general. Contemporary advancements in the field, such as lead-free positive temperature coefficient of resistivity effect materials and multilayer miniaturized systems based on hypostoichiometric barium compositions, are reviewed. Finally, perspectives on future lines of thermistor research, with a focus on the energy sector, are presented including applications in gas separation and chemical sensing.