A novel strategy to develop polysilanes functionalized with a high density of nonlinear optical chromophores has been explored. Thus a polysilane with phenyl and N,.N-dialkylsubstituted aniline as pendant groups was synthesized under standard conditions for the Wurtz reductive coupling, and the post azo coupling of p-nitrobenzenediazonium fluoroborate towards the aniline groups afforded a dispersed red (DR) chromophore-functionalized polysilane (P2). The poled film of P2 reveals a resonant d(33) value of 19 pm/V by second harmonic generation (SHG) measurements.