The exquisite combination of hetreometallic [TbIIINiII(COO)3(H2O)] clusters with a designed hexatopic ligand generates one highly robust three-dimensional heterometallic TbIII/NiII-organic framework material {[TbNi(HTDP)(H2O)]·3DMF·2H2O}n (NUC-2; H6TDP = 2,4,6-tri(2,4-dicarboxyphenyl)pyridine). Gas adsorption measurements reveal that the activated NUC-2 exhibits ultrahigh C2H2 adsorption capacity but negligible uptake of C2H4, which is ascribed to its high stability and ultrahigh functional internal surface. Furthermore, dynamic breakthrough experiments confirm that NUC-2 can effectively fulfill the separation of a C2H2/C2H4 (1 : 99) mixture. Such excellent performance makes NUC-2 a promising adsorbent for practical C2H2/C2H4 separation and provides new insights into heterometallic MOFs for gas separation.