Cyclic trimeric and high-polymeric phosphazenes bearing cinnamate groups were synthesized and characterized. Cyclic trimers with the general formula N3P3RyRx’ where R = OC6H4OC(O)CH=CHPh, R’ - OCH2CF3 (y = 1, x = 5 and y = 6, x = 0), and R = (OCH2CH2)2OC(O)CH=CHPh (y = 1, x = 5 and y = 6, x = 0) were synthesized. Also prepared were high-polymeric phosphazenes [NPR(x)R(y)’]n, where R = OC6H4OC(O)CH=CHPh, R’ = OCH2CF3 (y = x = 1 d y = 0, x = 2) and R = (OCH2CH2)2OC(O)CH = CHPh (y = x = 1 and y = 0, x = 2). The photo-cross-linking of a representative polymer was studied by UV spectroscopy.