Two novel organotin supramolecular coordination polymers (SCP), namely, 3∞[Me3SnCu(CN)2·(EN)2], 1 and 3∞[Ph3SnCu(CN)2·(3-mpy)2], 2 are obtained by the reactions of K3[Cu(CN)4], ethyl nicotinate (EN) or 3-methylpyridine (3-mpy) and Me3SnCl or Ph3SnCl in H2O/acetonitrile solution at room temperature. 2D-layers are constructed via H-bonds between the parallel 1D-puckered chains which contain nanometer-sized [–CN(R3Sn)NC-] spacers connecting the tetrahedral (T-4) copper sites. The network structures of 1 and 2 consist of infinite layers connected by interlayer H-bonds forming 3D-framworks. 2 is the first compound in this family containing the Ph3Sn cation. The electronic absorption spectra of 1 and 2 reveal a broad band at 320 nm due to CT transition while the emission spectra exhibit high energy bands at 400–460 nm due to metal-centered (MC) transitions and low energy bands at 485–530 nm corresponding to MLCT. The 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay was used to determine the in vitro antitumor effects of the SCP 1 and 2 on human breast cancer cell line, ZR-75-1. Cell cycle analysis revealed that the SCP 1 and 2 induced apoptosis in ZR-75-1 breast cancer cell line through activating caspase-3. Moreover, in vivo model, the compound SCP 2 suppressed tumor growth developed mammary carcinoma by 52.3%. Taken together, our novel compounds selectivity exhibit specific in vivo and in vitro antitumor effects.