Reasonable and high efficient utilization of carbon dioxide (CO2) has always been considered as a kind of green and sustainable development strategy. However, the efficient chemical conversion of CO2 into value-added products has been limited due to lack of efficient catalysts. Herein, two novel heterometallic hexanuclear complex catalysts (viz Nd4Zn2L2 (1) and Eu4Zn2L2 (2)) were designed and synthesized, which featuring unique hetero-multinuclear units. The heterometallic hexanuclear complex catalysts not only have multi-bimetallic catalytic sites (Ln3+ and Zn2+) which can absorb more molecules and be beneficial to the improvement of catalytic performance, but also have the potential to further expand the chemical fixation of CO2 with epoxides avoid the harsh reaction conditions. Using the synthesis of propylene carbonate (PC) by cycloaddition reaction of propylene oxide (PO) and CO2 as a model reaction, the as-prepared catalysts and catalytic system showed high turnover frequencies (TOFs) under the mild condition instead of harsh reaction conditions. More importantly, these catalysts can be reused to preserve the structure's integrity and retain their catalytic activity at the same level even after five rounds of catalysis. The excellent regeneration performance indicated that the as-prepared heterometallic hexanuclear complex catalysts can be reused many times. In addition, the catalytic system also exhibited a wide range of substrates for epoxide. These results predict that the proposed heterometallic hexanuclear complex catalysts and catalytic system have great potential toward CO2 adsorption and catalytic conversion. This work may build up a new synthetic route for tailoring more new heterometallic complex catalysts with excellent catalytic activity and applied in various fields of application.