Four novel polymeric coordination networks have been obtained through self-assembly processes involving alkoxo-bridged copper(II) species as nodes, and anionic cyano-complexes as linkers: ^∞₂[{Cu₂(pa)₂}{M(CN)₂}₂] (M = Ag, 1; Au, 2), ^∞₃[{Cu₄(mea)₄}{Au(CN)₂}₄·H₂O] 3, and ^∞₃[{Cu₂(pa)₂}{Ni(CN)₄}] 4 (pa = deprotonated propanolamine; mea = deprotonated monoethanolamine). The supramolecular architectures of compounds 1, 2 and 3 are sustained by argentophilic or strong aurophilic interactions. The solid-state architectures of 1 and 2, which are isomorphous, consist of infinite layers, constructed from binuclear alkoxo-bridged nodes and [M(CN)₂]⁻ spacers. The layers are stacked in an offset parallel mode, and are further interconnected through Ag⋯Ag or Au⋯Au contacts (1: Ag⋯Ag 3.015 Å; 2: Au⋯Au 3.069 Å). Compound 3 consists of unique fourfold interpenetrating diamondoid nets. The diamondoid topology is built of heterocubane {Cu₄O₄} nodes, which are connected by [Au(CN)₂]⁻ rods. The Cu–O distances within the {Cu₄O₄} node vary between 1.927(2) and 2.679(1) Å, showing unsymmetric bridging of the copper atoms. Aurophilic interactions are established between the bridging and terminal [Au(CN)₂]⁻ metalloligands, and connect the interpenetrating nets, resulting in infinite chains of gold atoms (the Au⋯Au distances vary between 3.253 and 3.305 Å). Compound 4 exhibits a 3-D network constructed from {Cu₂(pa)₂]²⁺ nodes connected by square-planar [Ni(CN)₄]²⁻ ions. Compounds 1, 2 and 4 are weakly paramagnetic. The cryomagnetic investigation of 3 reveals a gradual increase, followed by a decrease of the χ_MT product, as the temperature is lowered. A superposition of ferro- (J₁ = +20.8 cm⁻¹) and antiferromagnetic (J₂ = −6.4) interactions within the tetranuclear node was found. Antiferromagnetic interactions are established between the tetranuclear nodes (θ = −2.99 K).