This study reports the synthesis and characterization of two new Ag(I) and Cu(I)-based coordination polymers (CPs) with the chemical formulas of [Ag(bipp)(ClO4)]n (1, bipp = bis(4-pyridyl) propane) and [Cu2(bib)(CN)](NO3)(H2O)2 (2, bib = 4,4′-bisimidazolylbiphenyl). The molecular structures of the as-prepared CPs were determined by the single crystal X-ray diffraction studies and their phase purities have been confirmed via the power X-day diffraction analysis. The crystal structure analysis reveals that the both CPs reveal 1D chain-like structures and their frameworks are stabilized via the π–π interactions and H-bonding interactions. Furthermore, the size of the two CPs could be easily downsized into the nanometer via a simple reflux treatment. In connection to these, the as-prepared two nanostructural CPs were tested for their in vitro anticancer activities against three human brain tumor cell lines (SF17, SF767 and F126) via the MTT assay.