The dielectric and conductivity study of two series of five three-dimensional hybrid inorganic–organic networks as polymer electrolytes (3D-HION-APEs), with formula {Al[O(CH2CH2O)8.7] ρ /(LiClO4) z } n (1.86≤ ρ ≤2.24, 0≤ z ≤1.06) and {Zr[O(CH2CH2O)8.7] ρ /(LiClO4) z } n (1.81≤ ρ ≤1.99, 0≤ z ≤0.91) is presented. The real and imaginary components of the complex dielectric permittivity spectra ɛ * and conductivity spectra σ * are measured between −60°C and 80°C. Spectral analysis points out that the conductivity mechanism is determined by two dielectric relaxation events, α and β. The relaxation β occurs at higher frequencies than α, and is attributed to the segmental motion with characteristic frequency f seg. The relaxation α is attributed to the ionic motion with characteristic frequency f ion. The profiles of the direct conductivity σ dc and the frequencies f ion and f seg vs. the reciprocal temperature exhibit a Vögel–Tamman–Fülcher (VTF) behavior. The study of the activation energies of the dielectric relaxations α and β allows to determine their relative contribution to the direct conductivity σ dc at lower and higher temperatures. The dependence of the VTF parameters vs. the mole-to-mole ratios n Li/n O and n Li/n M (M=Zr, Al) in combination with previous equivalent conductivity studies, allows to identify the role of the ionic species and the metal nodes present in the polymer structure at various salt concentrations. The correlation between the diffusion coefficient D and the relaxation frequencies f seg and f ion of the 3D-HION-APEs is investigated.