By the combination of divergent and convergent approach, a new series of NLO dendrimers (G1-PFPh-NS-GL to G3-PFPh-NS-GL) was conveniently prepared with satisfied yields through the powerful “click chemistry” reaction, in which perfluoroaromatic rings were introduced in the periphery, two types of chromophores were arranged with regular AB structure, and their topological structure was improved to a more spherical shape. All the dendrimers demonstrated good processability, and G1-PFPh-NS-GL exhibited the highest NLO effect of 221 pm/V among the three dendrimers.Keywords: dendrimers; isolation chromophore; nonlinear optical (NLO) materials; the Ar/ArF self-assembly effect; “star-type” chromophore;