The synthesis, photophysical and nonlinear optical properties of several new multi-octupolar tris(bipyridine) ruthenium complexes are reported. The preparation on these complexes is based on the initial construction of multipodal 4,4'-dialkylaminostyryl-2,2'-bipyridine ligands (DAAS-bpy). Thermally stable polyimides featuring octupolar ruthenium trisbipyridyl complexes have been readily obtained by a polycondensation reaction. The controlled coordination strategy of dipodal and tripodal bipyridines to ruthenium(II) has also been successfully used to build bimetallic, trimetallic as well as the first metallodendrimer made of seven metallo-octupoles. These polymetallic species exhibit very intense absorption bands in the visible and long-lived luminescence. The quadratic NLO-susceptibilities beta of these macromolecules have been characterized by harmonic light scattering at 1.91 mum and compared with those of the corresponding monometallic species. The NLO studies clearly demonstrates a quasi-supramolecular ordering in the metallodendrimer.