Abstract: | 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 d33 value of 19 pm/V by second harmonic generation (SHG) measurements. |