A pair of novel chiral compounds based on homochiral 8-fold interpenetrated metal-organic frameworks (MOFs) and chiral polyoxometalates (POMs), formulated as D-[Cu(4,4' biPY)(1.5)](4)[Mo8O26] (D-1) and L-[Cu(4,4'-nbipy)(1.5)](4) [Mo8O26] (L-1) (4,4'-bipy = 4,4'-bipyridine), have been successfully synthesized and characterized by single crystal X-ray diffraction, infrared, thermogravirnetric analysis, elemental analysis, and solid circular dichroism spectra. Structural analysis indicates that two compounds are enantiomers. The connection of copper cations and 4,4'-bipy ligands generates helical infinite chains, while adjacent chains are further linked by Cu-N bonds to form a three-dimensional interpenetrating framework with a (10,3)-a topology. Interestingly, the chiral [Mo8O26](4-) polyanions are encapsulated in the chiral MOFs via sharing the oxygen atoms. Both D- and L-[Cu(4,4'-bipv)(1.5)](4)[Mo8O26] crystallize in chiral space group C222(1). Additionally, two compounds represent new examples of chiral self-assembly.