Aqueous reactions of copper(I) cyanide with 1-phenylpiperazine (PhPip) in the presence of KCN produce network compounds having CuCN:PhPip stoichiometries of 1:1, 3:2, and 4:1 depending on the mixing ratio used. In addition to these phases, hydrothermal synthesis yields a 5:3 network. Crystal structures of these four compounds are reported herein. The (CuCN)(PhPip) network (1) forms sheets consisting of Cu centers that coordinate all PhPip via NH only, and are linked together by μ3-cyano bridges. The (CuCN)3(PhPip)2 network (2) exists as a series of dual-chain ladders. All Cu centers are 3-coordinate and half of the PhPip ligands bridge pairs of chains using both NH and NPh, while the other PhPip are only NH bound. The (CuCN)5(PhPip)3 network (3) forms three independent sets of 1D chains: 2[(CuCN)(PhPip)]·(CuCN)3(PhPip). Both 2- and 3-coordinate copper atoms are present and all PhPip ligands bond only through NH. The (CuCN)4(PhPip) network (4) forms identical, but orthogonal, interpenetrating sheets consisting of 2- and 3-coordinate CuCN chains linked by bridging PhPip ligands. Pairwise cuprophilic interactions are seen in the 5:3 and 4:1 networks. The 3:2 compound shows visible photoluminescence associated with Cu-CN MLCT. Compound 1 crystallizes in the monoclinic P21/c space group with cell parameters: a = 17.6123(3) Å, b = 6.89480(10) Å, c = 8.6154(2) Å, β = 96.1460(10), V = 1040.18(3) Å3, and Z = 4. Compound 2 crystallizes in the triclinic P − 1 space group with cell parameters: a = 9.93710(10) Å, b = 10.6359(2) Å, c = 12.1230(2) Å, α = 105.7110(10), β = 100.6110(10), γ = 97.7230(10), V = 1189.11(3) Å3, and Z = 2. Compound 3 crystallizes in the monoclinic P21/n space group with cell parameters: a = 15.9018(2) Å, b = 9.38850(10) Å, c = 26.1864(3) Å, β = 104.5110(10), V = 3784.76(8) Å3, and Z = 4. Compound 4 crystallizes in the monoclinic P21 space group with cell parameters: a = 13.4773(3) Å, b = 7.8460(2) Å, c = 8.5527(2) Å, β = 105.1820(10), V = 872.82(4) Å3, and Z = 2.