A series of PTC thermistors, based on BaTiO3, doped with Ca, Mn and Y, were prepared with additions of SiO2 at levels of 0, 1, 2 and 3 at. %. The effect of the SiO2 additions and cooling rate on microstructural development and bulk performance were characterised using a combination of SEM, EBSD, and R-T experiments. It was found that the addition of SiO2 increased grain size marginally, and decreased sample density by reducing the amount of grain-grain contact. The addition of SiO2 also modified the distribution of grain boundary types by systematically decreasing the proportion of low-Σ grain boundaries within the microstructure. Electrical behaviour was modified by adding SiO2 or increasing the sample cooling rates; in both cases there was an increase in ρ25 and a decrease in ρmax, with ρmax also being displaced to higher temperatures.