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A variety of novel poly[ethynediyl-arylidene-ethynediyl-silylene]s (PEAES), including those containing hypercoordinate silicon atom as well as donor and acceptor groups, has been synthesized. The presence of hypercoordinate silicon favours high values of fast Kerr-type non-linearities, and the incorporation of amide groups gives rise to good optical quality nanocomposites in a silica matrix. The inorganic-organic hybrid sol-gel film incorporating 5–14 mass% of the polymer containing pentacoordinate silicon showed Reχ (3) = −9.5 ×10−11 esu. The predominant rôle of the electron nonlinear mechanism has been demonstrated by using test beams with linear and circular polarizations. The photorefractive properties of composites based on PEAES as optical chromophores, poly(9-vinylcarbazole) as photoconductor, N-ethylcarbazole and phenyltrimethoxysilane as plasticizer, and fullerenes as charge generators have been investigated. The nonlinear optical effects, including four-wave mixing and two-beam coupling were studied at 633 nm without preliminary electric poling. The photorefractive origin of the refractive index changes was confirmed by the high two-beam gain under an externally applied electric field. Refractive index gratings affording two-beam gain can also be written under zero field conditions. To explain this unique property of the materials it is suggested that chromophore orientation asymmetry arises either during film formation or is induced by the longitudinal intensity gradient.