New single-ion hybrid electrolytes have been synthetized via an original and simple synthetic approach combining Michael addition, epoxidation, and sol–gel polycondensation. We designed an organic PEO network as a matrix for the lithium transport, mechanically reinforced thanks to crosslinking inorganic (SiO1.5) sites, while highly delocalized anions based on lithium vinyl sulfonyl(trifluoromethane sulfonyl)imide (VSTFSILi) were grafted onto the inorganic sites to produce single-ion hybrid electrolytes (HySI). The influence of the electrolyte composition in terms of the inorganic/organic ratio and the grafted VSTFSILi content on the local structural organization, the thermal, mechanical, and ionic transport properties (ionic conductivity, transference number) are studied by a variety of techniques including SAXS, DSC, rheometry, and electrochemical impedance spectroscopy. SAXS measurements at 25 °C and 60 °C reveal that HySI electrolyte films display locally a spatial phase separation with domains composed of PEO rich phase and silica/VSTFSILi clusters. The size of these clusters increases with the silica and VSTFSILi content. A maximum ionic conductivity of 2.1 × 10−5 S·cm−1 at 80 °C has been obtained with HySI having an EO/Li ratio of 20. The Li+ ion transfer number of HySI electrolytes is high, as expected for a single-ion electrolyte, and comprises between 0.80 and 0.92.