A new 3D-host-guest supramolecular coordination polymer (SCP); ∞3[(Cu3(CN)3)2.(DAHP)], 1 [1,7-diaminoheptane=.(DAHP)] had been synthesized by self-assembly at ambient conditions. X-ray single crystal diffraction of SCP 1 indicated the formation of two-fold [Cu3(CN)3]2 units containing tetrahedral copper(I) atoms which are arranged in unique way to create 3D-network. The neutral [Cu3(CN)3]2 building blocks create unique complex structure containing the minicycle [Cu2(μ3-CN)2] motif with wide cavities enable to capsulate the long chain DAHP as guest molecule. The topology of 1 had been studied by elemental analysis, IR-spectra and thermogravimetric analyses. The topology of 1 had been compared with the prototype SCP containing different aliphatic diamines which indicated the effect of structural variability and flexibility of aliphatic diamines on the network structure of these SCP. The catalytic and photo-catalytic activity of 1 was studied for mineralization of methylene blue (MB) utilizing H2O2 as an oxidant.