AbstractA new photocrosslinkable polymer designed for application in second harmonic generation has been prepared and tested for frequency doubling of IR lasers. The polymer is based on a colorless polyurethane with pendant tolane nonlinear optical chromophores that carry a polymerizable styrene moiety at their extremities. Photocrosslinking is achieved by irradiation of films containing a small amount of a bleachable radical photoinitiator. The effect of photoinduced radical crosslinking on the mobility of the chromophores has been studied by recording the intensity of the frequency doubled light, generated by a poled sample, with increasing temperature. As expected, photocrosslinking leads to NLO materials with highly stable chromophore orientation.