With the aim to make the influence of pentafluorophenyl groups in the periphery of high generation dendrons and dendrimers on their NLO performance clearly, some NLO dendrons and dendrimers with different chromophore moieties or different end-capped groups were carefully designed and investigated in detail. The results demonstrated that some strong Ar-Ar(F) interactions between the pentafluorophenyl groups in the periphery and the normal phenyl rings of the donors, could influence the topological structures of dendrons or dendrimers, and then affect their NLO performance. Furthermore, the optical transparency and the stability of the dendrons and dendrimers with pentafluorophenyl groups as end-capped moieties were all improved, in comparison with normal dendrons and dendrimers containing phenyl ones as the end-capped groups.