In the paper, the electrical properties of crystalline LiCl-noncrystalline Li2O·3B2O3 composite Li ionic conductor are studied. Some new phenomena of changes in electrical properties of this composite ionic conductor have been found, i.e. a "two-peak" effect of conductivity enhancement appears on macroscopic conductivity σm versus composition curve. Correspondingly, "two-valley" appears on apparent activation energy Em versus composition and dielectric constant εm versus composition curve. These experimental phenomena have been discussed in detail, and the results are consistent with conduction theory.