Zn-Ni-Ti-O system ceramics were prepared by solid state reaction method using two different routes. The positive temperature coefficient of resistivity (PTCR) behavior and microstructure were investigated in terms of different composition and synthetic routes. It was found that using ZnO, NiO and TiO2 as the starting materials (route A), the prepared ceramics exhibited low room temperature resistivity (ρRT was ~102 Ω•cm) and inferior resistivity jump (ρmax/ρmin<50) starting at the temperature when it began to rise. However, using ZnOss (Zn0.95Ni0.05O), NiOss (Ni0.55Zn0.45O) and spinel phase (ZnNiTiO4) as starting materials (route B), the ceramics revealed ρRT >103 Ω•cm and marked resistivity jump (ρmax/ρmin was ~102) starting at ~200 °C. The microstructure showed that the ceramics prepared by route B possessed clear-cut grain boundaries but the grains of ceramics prepared by route A were irregular shape and distribution.