This work has demonstrated that the addition of specific amount of poly(oxypropylene) diamine (d2000) and mineral clay in the PEO-based electrolyte system can form the high conductivity film at room temperature. Specific interactions among silicate layer, d2000, ether oxygen, and lithium cation have been investigated using differential scanning calorimetry (DSC), alternating current impedance (AC impedance) and Fourier-transform infrared (FT-IR). The DSC characterization confirms that the addition of 25 w1% d2000 is able to produce low T-g and fully amorphous (PEO)(8)LiClO4/d2000 electrolyte system which produce the good environment for ionic transfer. Additionally, the incorporation of the mineral clay into the (PEO)(8)LiClO4/d2000 electrolyte system can sustain the polymeric mechanical property by its huge surface area and enhance the conductivity due to the specific interaction between silicate layers and lithium cation. FT-IR spectra confirm that the incorporation of the clay is able to dissolve the lithium salts more effectively and resulting to the higher fraction of free anions due to the strong interaction between negative charges of the silicate layers and lithium cations of the lithium salt.