Replacing the benzene spacer in the organic linker 5,5'-(benzene-1,4-diyl)diisophthalate with the nitrogen containing heterocyclic rings, namely, pyrazine, pyridazine, and pyrimidine results in three organic linkers, which were reacted with copper ions under solvothermal conditions to form three isostructural metal-organic frameworks (ZJNU-46, ZJNU-47 and ZJNU-48) exhibiting exceptionally high sorption capacities with regard to acetylene due to the simultaneous immobilization of open metal sites and Lewis basic nitrogen sites in the frameworks. At 1 atm and 295 K, the gravimetric C2H2 adsorption uptakes reach 187, 213 and 193 cm(3) (STP) g(-1) for these three compounds. The gravimetric C2H2 adsorption amount of ZJNU-47a is the second highest reported for MOF materials. Notably, despite their same porosities, and densities of open metal sites and uncoordinated nitrogen sites, distinctly different C2H2 adsorption capacities were observed for these three compounds, which we think are mainly associated with the difference in the relative position of nitrogen atoms leading to different binding affinities of the frameworks towards C2H2 guest molecules, and thus different C2H2 adsorptions. This work demonstrates that the rational arrangement of open nitrogen sites will favorably improve the C2H2 uptake and thus provides useful information for future design of porous MOFs with high acetylene storage capacities.