Li5La3Ta2O12 (LLTa) is a promising solid electrolyte for all-solid-state batteries due to its high stability in contact with Li metal, however, low Li ion conductivity of LLTa has restricted its application. In this study, improvement of the Li ion conductivity of LLTa solid electrolyte by substitution of Ge4+ for Ta5+ is studied because the improvement is thought to be achieved by increase of charge carrier concentration caused by the substitution of low valence Ge4+ for high valence Ta5+. The Ge substitution shrinks a lattice of cubic LLTa due to small ion radius of Ge4+ (0.530 Å) compared with Ta5+ (0.640 Å). The Li ion conductivity of LLTa is improved by the Ge substitution. The highest bulk and total Li ion conductivities are obtained in Li5.25La3Ta1.75Ge0.25O12 prepared by spark plasma sintering at 1100 °C and the values are 1.3 × 10−4 and 8.4 × 10−5 S cm−1 at 28 °C, respectively. The lithium transference number of the Ge-substituted LLTa determined by Hebb-Wagner (HW) polarization method is ≈ 1. Also, it is verified that the new solid electrolyte is stable in a potential range of 0–10 V vs. Li/Li+, indicating that the Ge-substituted LLTa is a promising solid electrolyte for all-solid-state battery application.