A 3D heterothiometallic cluster-based metal-organic framework was constructed from the new oligomeric decanuclear heterothiometallic building clusters [W-2(mu(3)-S)(6)(mu(4)-S)(2)Cu-8](4+), tetra-dentate 3-abpt units (3-abpt = 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole), and CN- bridges. It possesses an unprecedented (3,11)-connected architecture, luminescence, and highly sensitive 2,4,6-trinitrophenol (TNP) sensing properties in both organic and aqueous media.