The preparation of P(o-MAABA) via ATRP and the composite of P(o-MAABA)/ZnO nanoparticles were described. 1H NMR, IR, TA and TEM were utilized to confirm the results. 1H NMR indicates that the structure of the P(o-MAABA) was definite, and the molecule weight of P(o-MAABA) was 7900. IR shows that ZnO nanoparticles were introduced to P(o-MAABA) and were interacted with the reactive groups of polymer. TA shows that the heat stability of P(o-MAABA))/ZnO composite increased greatly. TEM photo demonstrates that the composite was spherical and the surface was smooth. The P(o-MAABA)/ZnO composite exhibits particular fluorescence property, and the emission spectrum of the P(o-MAABA)/ZnO composite red shifts 25 nm compared to the polymer. In addition, the composite features good solubility and film formability, and may become a new optical material.