Li3-2xMxInBr6 (M=Mg, Ca, Sr and Ba) and Li3In1-xMxBr6 was synthesized, and thier substitution effect was investigated by means of 7Li and 115In NMR, X-ray diffraction and AC conductivity measurements. Phase transition was observed at 314 K in Li3InBr6 and fast Li+ diffusion was observed in the high temperature phase. Li3InBr6 has high Li+ ion conductivity and showed a little difference in X-ray diffraction patterns between the low-temperature phase and the high-temperature phase. These indicate that the sub-lattice for Li+ ions changed largely at the phase transition point and this change makes Li+ diffusion easily. In the high temperature phase of substituted compounds, the conductivity decreased with the amounts of substitution. and defects produced by the substitution with divalent cation did not contribute to the Li+ ion conduction. In the LT phase for Mg compound, the ionic conductivity increases up to x = 0.4 due to the introduction of the extrinsic vacancies.