Anion binding and extraction from solutions is currently a dynamic research topic in the field of supramolecular chemistry. A particularly challenging task is the extraction of anions with large hydration energies, such as the carbonate ion. Carbonate-binding complexes are also receiving increased interest due to their relevance to atmospheric CO2 fixation. Nanojars are a class of self-assembled, supramolecular coordination complexes that have been shown to bind highly hydrophilic anions and to extract even the most hydrophilic ones, including carbonate, from water into aliphatic solvents. Here we present an expanded nanojar that is able to bind two carbonate ions, thus doubling the previously reported carbonate-binding capacity of nanojars. The new nanojar is characterized by detailed single-crystal X-ray crystallographic studies in the solid state and electrospray ionization mass spectrometric (including tandem MS/MS) studies in solution.