A click polymer reaction was demonstrated to attach highly polar nonlinear optical (NLO) azo chromophores to azido-containing poly(1-phenyl-1-pentyne). The reaction was monitored by Fourier Transform Infrared (FT-IR) spectroscopy as the axido groups absorb strongly centered at 2096 cm<sup>-1</sup> and the reactions proceed completely in 2 h, indicated by the disappearance of the peak 2096 cm<sup>-1</sup>. The results show that when polymer isolation groups change from hydrogen atom to the phenyl group, the value of polymer increase to 1.8 times. The introduction of different isolation groups lead to different molar weights of obtained chromophore moieties, resulting in dilute concentration of the active chromophore moieties in the polymers....