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Research on doping modification of ZnTiO3 ceramics to enhance microwave dielectric properties has been hindered by poor performance, unclear structure-function mechanisms. To expand the applicability of ZnTiO3 ceramics, this study explores Zn1–xLi2xTiO3 (0 ≤ x ≤ 1) ceramics using a phase engineering strategy. Our findings reveal that the introduction of Li+ into the ZnTiO3 system initiates a multiple phase transition, starting at x = 0.1. Initially, ilmenite ZnTiO3 transforms into a cubic ordered spinel phase (space group P4332). Subsequently, a transition to a disordered spinel phase (space group Fd
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