Mixed linker metal–organic polyhedra (MOPs) with polar and non-polar groups on the same MOP have been synthesized. This yields two types of MOPs, one where the ligands are evenly and symmetrically distributed over each polyhedron, as confirmed crystallographically and the other where respective groups segregate. The segregation is confirmed by the amphiphile-like behavior of the latter MOP in different polarity solvents, as seen through transmission electron microscopy (TEM) even though the anchor points of the functional groups are ∼10 Å apart on the MOP surface.