The synthesis and characterization of linear poly(ether 1,2-glycerol carbonate)s derivatized with pendant butyl, octyl, or stearyl tethers are reported. The polymers are obtained via the ring-opening copolymerization of butyl, octyl, or stearic glycidyl ethers with carbon dioxide using the [rac-SalcyCoIIIDNP] catalyst bearing a quaternary ammonium salt. Synthesized polymers were characterized by 1H and 13C NMR spectroscopy, FT-IR, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and rheometry. Polymers with controlled molecular weights in the range of 8970–31 900 g/mol were obtained with low polydispersities between 1.1 and 1.4. Thermal properties of the materials confirm amorphous structures of the polymers with butyl and octyl chains, with glass transition temperatures of −24 and −34 °C, respectively. The stearyl tether polymer exhibited a melting point of 55 °C. Additionally, the potential of poly(butyl ether 1,2-glycerol carbonate) as a thermally stable solid polymer elect...