A series of novel polymers having polar azo dyes were synthesized and characterized. Although their chromophore contents are very high, their second order nonlinear (2-NLO) response was very poor. The poor 2-NLO responses are thought to be due to poor orientation because of their improper main chain conformations, as well as their low glass transition temperatures. They undergo slow cross-linking on standing at room temperature, and rapidly on heating at temperalures above 150degreesC, through the diacetylene units of the main chains. Nevertheless, these polymers are interesting materials as azo-polymers because of their very high concentration of azo dyes, which are distributed homogeneously in the polymers. Synthesis and characterization are described, and the most important factor for the 2-NLO polymers is discussed.