Reactions of two preformed trinuclear W/Cu/S clusters, [A](2)[WS4(CuCN)(2)] (1: A = Et4N; 2: A = PPh4) with different concentrations of acetic acid in MeCN generate two interesting 2D polymeric clusters [Et4N](3)[(WS4Cu2)(2)-(u-CN)(3)](.)2MeCN (3), and [PPh4][WS4Cu3(μ-CN)(2)](MeCN)-Me-. (4), respectively. Compound 4 can also be readily obtained in a high yield from the reaction of 2 with equimolar [Cu(MeCN)(4)]PF6 in MeCN. These compounds have been characterized by elemental analysis, IR spectra, thermal analysis, and single-crystal X-ray diffraction. An X-ray analysis reveals that compound 3 retains the WS4Cu2 cluster core, which serves as a 3-connecting node to link equivalent nodes via single cyanide bridges, forming an anionic 2D (6,3) net. Compound 4 consists of a T-shaped WS4Cu3 core, which also acts as a 3-connecting node, with links to 3 equivalent clusters either through single or double cyanide bridges, affording a different anionic 2D (6,3) network. The acetic acid induced aggregation of 3 and 4 from the two cluster precursors 1 and 2 suggests that this simple synthetic strategy is likely to be applicable to many related systems.