To develop more “H”-shape nonlinear optical polymers, in this paper, four new polymers embedded with “H”-type chromophore moieties were designed and synthesized through a Suzuki coupling copolymerization reaction. The “H”-type chromophores were easily prepared by the utilization of “Click Chemistry” reactions, and their structures could be conveniently adjusted by changing the diazido groups. All the polymers exhibited good film-forming ability, thermal stability, and large optical nonlinearities. As a typical example, P4 demonstrated the highest d33 value of 94.7 pm/V, and its onset temperature for decay was up to 103 0C, making it promising candidate for practical applications in photonic fields.