The assembly of a tetradentate pyridine-derived ligand with CuX has afforded two isostructural Cu(I)-organic frameworks [Cu2X2(TBD)·DMF]n (X = Cl for 1 and Br for 2) in this work. Structural analysis indicates that the compounds feature hybrid layered architectures, and the three-dimensional supramolecular frameworks are finally fabricated through the alternative stacking of adjacent layers wherein large open channels are simultaneously constructed. The chemical stability has been studied showing the excellent skeleton maintenance of the prepared solids in various solvents and even in water. Moreover, the iodine and dye sorption performance for compound 1 has been further tested. The Cu(I)-based metal-organic framework exhibits outstanding sorption and separation abilities on the targeted species, which could be considered as a promising adsorbent with high efficiency and selectivity.