Ge-doped LiTi₂(PO₄)₃ has been synthesized by a conventional solid-state reaction. Compounds LiM₂^IV(PO₄)₃ with LTP-type structure present a different behaviour depending on nature of M^(IV). For M^(IV) = Ti and Ge, the structure shows the space group R3c, whereas for M^(IV) = Ge the space group is R3. Differences in behaviour of LiTi₂(PO₄)₃-LiGe₂(PO₄)₃ solid solutions are discussed in relation to the composition. Their structures LiTi_2-xGe_x(PO₄)₃ (0≤ x<2) were determined from X-ray powder diffraction method (XRD) using Rietveld analysis. A sharp change in the lattice parameter a is observed between the compositions with x=1. The lattice parameter c increases as the Ge content increases in the whole range of composition. The space group R3c becomes R3 for the composition with x>1. The SEM micrographs of the samples show relative porous microstructures due to the effect of the substitution. Keywords: NASICON, origin of unusual evolutions of lattice parameters, phase transition, scanning electron microscopy SEM, X-ray diffraction DRX, Rietveld refinements

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