Chemical fixation of carbon dioxide (CO2) is an energy-saving method for alleviating the greenhouse gas emissions, whereas it persists a challenge posed by the demand for efficient catalysts. Herein, four unprecedented examples of tetradecanuclear vanadium clusters, namely, [(C2H8N2)6(CH3O)8(CH3OH)2VIV10VV4O26] (V14−1), [(C3H10N2)6(CH3O)8(CH3OH)2VIV10VV4O26](V14−2), [(C6H14N2)6(CH3O)8(CH3OH)2VIV10VV4O26]·5H2O (V14−3) and [(C4H12N2O)4(C4H11N2O)2(CH3O)2VIV10VV4O28]·6H2O (V14−4), have been triumphantly designed and constructed under solvothermal conditions. Among them, compounds V14−1–4are the first cases of tetradecanuclear vanadium clusters without the introduction of inorganic acid radical ions. Two main units [VIV10VV4O26]8+and [VIV10VV4O28]4+represent brand-new configurations of tetradecanuclear vanadium clusters. Given the fact that the presence of VIV/VVcan potentially facilitate electron transfer and consequently expedite catalytic reactions, we explored the catalytic activities of these compounds. Remarkably, V14−1was further used as a heterogeneous catalyst in the CO2fixation into cyclic carbonates under milder conditions (60 °C, 0.5 MPa) and exhibited higher catalytic activity. Also, the experimental results indicated that V14−1could efficiently catalyze the sulfoxidation, which could fully convert most sulfides within 40 min at room temperature. Moreover, as a stable heterogeneous catalyst employed in CO2fixation with epoxides and oxidation of sulfides, V14−1could be consecutively used multiple cycles without losing its catalytic activity.