The combination of copper perchlorate, 2,3-pyrazinedicarboxylate (pzdc) and one of pyrazine (pyz), 4,4'-bipyridine (bpy), or trans-1,2-bis(4-pyridyl)ethylene (bpe) yields a series of Cu complex-assembled compounds [Cu-2(pzdc)(2)(PL). xH(2)O](n) (PL = pyz, bpy, or bpe). These compounds were characterized by elemental microanalysis, X-ray diffraction, thermogravimetric analysis, and gas adsorption. The XRD data show that the Cu complex-assembled solids possess a three-dimensional structure with one-dimensional semi-rectangular channels; the fixed width of the rectangular micropores is 6 Angstrom and the ether width varies from 4 to 11 Angstrom with the length of ligand. The microporosity of the compounds was confirmed by N-2, Ar, and CO2 adsorption. Dudinin-Radushkevich plots of the adsorption isotherms provided that the micropore volume for each compound changes with the different adsorbate, indicating the presence of the molecular geometry-sensitive micropore filling. Also we observed that the rectangular micropore has a deeper potential well than the slit-shaped pores of activated carbon fibers.