Poly(phenazasiline)s (PPhenaz) and related phenazasiline copolymers having arylenediethyndiyl units in the backbone (PPhE) were prepared by organometallic processes. PPhenaz films show reversible electrochromic behavior upon electrochemical treatment. A double layer electroluminescent device comprising PPhenaz with n-C8H17 groups bound to the silicon displays high performance similar to those comprising a typical hole-transport material, poly(N-vinylcarbazole).