Organic–inorganic hybrid electrolytes based on di-ureasil backbone structures by reacting poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether) (ED2000) with 3-(triethoxysilyl)propyl isocyanate (ICPTES), followed by co-condensation with methoxy(polyethylenoxy)propyl trimethoxysilane (MPEOP) in the presence of LiClO4 were prepared and characterized by a variety of techniques. The hybrid electrolytes showed good resistance to crystallization and excellent conductivity for use in lithium-ion batteries, as determined by differential scanning calorimetry (DSC) and impedance measurements, respectively. The temperature dependence of the ionic conductivity exhibited a VTF (Vogel–Tamman–Fulcher)-like behavior for all the compositions studied and a maximum ionic conductivity value of 6.9×10−5 Scm−1, a relatively high value for solid polymer electrolytes, was achieved at 30°C for the hybrid electrolyte with a [O]/[Li] ratio of 16. A microscopic view of the dynamic behavior of the polymer chains (13C) and the ionic species (7Li) was provided by the 1H and 7Li line widths measured from 2D 1H–13C WISE (Wideline Separation) and variable temperature 7Li static NMR, respectively, to elucidate the influence of the mobility of the polymer chains and the charge carriers on the observed ionic conductivity. The present salt-free hybrid electrolyte after plasticization with 1M LiClO4 in EC/PC solution exhibited a swelling ratio of 275% and reached an ionic conductivity value up to 8.3×10−3 Scm−1 at 30°C, which make it a good candidate for the further development of advanced rechargeable lithium-ion batteries.