A new type of high photosensitive azo functional polymers was synthesized and characterized by viscometry, infrared (IR) spectroscopy and Raman spectroscopy. Xerographic properties were determined in bilayer devices. Results show that azo polymers have high photosensitivity resulting from the high electronic mobility (AP-1 and AP-3) and a high charge transfer (AP-4). The study of spectral responses indicates that these polymers exhibit good xerographic properties in visible region, and AP-1 also has high photosensitivity in the near-IR region.