In the present work, the hyper-branched (HB) polymer is utilized as a host material to efficiently incorporate the nonlinear optical chromophore. The HB polymer and toluene diisocyanate (2, 4-TDI) formed 3-D networks, and the typical FTC or CF3-Ph-FTC chromophores were introduced to investigate the electro-optic activity (r33). At the same time, poling behavior of NLO chromophores in the traditional poly methyl methacrylate (PMMA) and Poly MMA-MOI side-chain polymers were also included in this work for comparison. For FTC doped composites, the r33 reached over 80 pm/V in 3-D network matrix, while the value of r33 maximized at about 45 pm/V in traditional PMMA host and 70 pm/V in side-chain polymers. In addition, the measurement of poling process, poling efficiency, and thermal stability for the real application were also investigated.