Vanadium(V) complexes derived from aminotriphenolate ligands are demonstrated to be highly active catalysts for the coupling of various terminal and internal epoxides with carbon dioxide to afford a series of substituted organic carbonates in good yields. Intriguingly, a V(V) complex bearing peripheral chloride groups on the ligand framework allowed for the formation and isolation of a rare complex that incorporates a ring-opened epoxide with one of the phenolate-O atoms acting as a nucleophile and the metal center as a Lewis acidic site. This unusual structure was characterized by X-ray diffraction and ⁵¹V NMR and was shown to exhibit catalytic activity for the coupling of propylene oxide and CO₂ when it was combined postsynthetically with these substrates. The results obtained herein clearly show that vanadium complexes in a high oxidation state are effective catalysts for the activation of challenging internal epoxides and their conversion into cyclic organic carbonates.