A new MOF, [Zn4O{Cu(L)2}2] (1), with a 4-fold interpenetrated 3D diamondoid structure was synthesised from in situ generated [Cu(L)2] NHC linkers. MOF 1 possesses tetrahedral Zn4O nodes, which are unusually coordinated by four pairs of carboxylates from four [Cu(L)2] linkers, and 14 Å 1-D pore channels lined with [Cu(L)2] moieties that catalyse the hydroboration of CO2.