Five- and six-membered bicyclic carbonates are valuable raw materials for the synthesis of environmentally friendly polymers, such as polycarbonates or non-isocyanate poly(hydroxyurethane)s. However, bicyclic diglycerol dicarbonates bearing five-membered and six-membered rings have been never reported before. In this work, for the first time, we report a simple procedure for the synthesis of this monomer from commercially available diglycerol. The product was characterised by ¹H NMR, ¹³C NMR, FTIR spectroscopy and X-ray diffraction measurements. Next, the reactivity of the obtained bicyclic carbonate was investigated. The obtained diglycerol dicarbonate was used as a monomer for polycarbonate and non-isocyanate poly(hydroxyurethane) based on putrescine. In the homopolymerisation reaction the opening of the six-membered carbonate ring was observed, while in the polycondensation with diamine both carbonate rings open nonselectively.