A 3D metal–organic framework,{[WS4Cu4 (dpbp) 4] 2+·[WS4Cu3 (dpbp) 2I2]−· I−} n· xSolvent,[dpbp= 4, 4′-di (4-pyridyl) biphenyl] with an unprecedent 8-fold non-equivalent interpenetration mode is presented, which contains four anionic and four cationic frameworks formed by tetranuclear [WS4Cu3I2]− and pentanuclear [WS4Cu4] 2+ SBUs with long dpbp ligands. Large rhombus-shaped tubes with diagonal dimensions of∼ 20× 10 Å ...