The immense potential of colossal permittivity (CP) materials for use in modern microelectronics as well as for high-energy-density storage applications has propelled much recent research and development. Despite the discovery of several new classes of CP materials, the development of such materials with the required high performance is still a highly challenging task. Here, we propose a new electron-pinned, defect-dipole route to ideal CP behaviour, where hopping electrons are localized by designated lattice defect states to generate giant defect-dipoles and result in high-performance CP materials. We present a concrete example, (Nb + In) co-doped TiO2 rutile, that exhibits a largely temperature-and frequency-independent colossal permittivity (>10(4)) as well as a low dielectric loss (mostly <0.05) over a very broad temperature range from 80 to 450 K. A systematic defect analysis coupled with density functional theory modelling suggests that 'triangular' (In23+VoTi3+)-Ti-center dot center dot and 'diamond' shaped Nb(2)(5+)Ti(3+)CA(Ti) (A+Ti3+/In3+/Ti4+) defect complexes are strongly correlated, giving rise to large defect-dipole clusters containing highly localized electrons that are together responsible for the excellent CP properties observed in co-doped TiO2. This combined experimental and theoretical work opens up a promising feasible route to the systematic development of new high-performance CP materials via defect engineering.