A series of 1,3,5-tricyano-2,4,6-tris(styryl)benzene derivatives (1,2) and dendrimers (3) have been synthesized and their first hyperpolarizabilities (β) were determined. Whereas the λmax values of 1–3 are similar, the oscillator strength increases with the molecular size. For all compounds, the Stokes shifts are significantly larger when NAr2 is used as the donor. The β(0) values of 1–3 range from 252 to 507 × 10–30 esu and increases with the number of octupolar units in the molecule. When the octupolar molecules are linked to the 1,3,5-position of the benzene ring by flexible ether linkages, the β(0) value increases by 1.7 fold. On the other hand, octupolar monodendron based on the nitrogen atom core and 1,3,5-tricyano-2,4,6-tris(p-diarylaminostyryl)benzene moieties at the periphery exhibits β(0) = 507 × 10–30 esu, which is one of the largest β(0) values reported for the octupolar molecules.