A novel sandwich‐type complex [Na(H2O)4][{Na3(H2O)5}{Mn3(bpp)3} (SbW9O33)2}]·8H3O (MnSbW‐bpp) (bpp = 1,3‐bis(4‐pyridyl) propane) is synthesized and characterized by elemental analysis, IR, thermogravimetric analysis, and single‐crystal X‐ray diffraction. The MnSbW‐bpp compound is the first sandwich case bridged by a flexible ligand. Its biological function of MnSbW‐bpp in antitumor activity is also determined in vitro and in vivo. The inhibitory proliferation and induction of apoptosis are performed by flow cytometry assay, S180 (sarcoma) tumor xenograft in ICR mice, the color Doppler ultrasound monitor, and TdT‐mediated dUTP‐biotin nick end labeling assay. The results show that the novel compound—MnSbW‐bpp—is synthesized and identified by its physical and chemical characteristics, such as the fluorescent and paramagnetic activities. MnSbW‐bpp indicates a potency inhibition of human cancer lines, such as SGC‐7901, HT‐29, HepG2, Hela, U2OS, SaoS2, and HMC cells. MnSbW‐bpp also inhibits the growth of tumor xenograft in mice, induced cell apoptosis, and released cytochrome c in vivo and in vitro. Thus, MnSbW‐bpp, as a new compound, possesses the potent inhibition of cancer cells, which indicates that the MnSbW‐bpp has potential merit for the further evaluation of a novel antitumor agent.