A derivative of poly(p-phenylene ethynylene) was subjected to the palladium-catalyzed three-component coupling reactions with aryl halides and phenylboronic acid to obtain polymers having tetrasubstituted cis-vinylene units. For example, 69% of the acetylene units in the prepolymer were converted to cis-vinylene (i.e., tetrasubstituted cis-vinylene) units using iodobenzene and phenylboronic acid (5 equiv each with respect to acetylene units). In the UV-vis absorption spectra of the resulting polymers, clear hypsochromic shifts of the absorption maxima were observed, while bathochromic shifts and suppression of the efficiency were observed in their photoluminescence spectra. (C) 2015 Wiley Periodicals, Inc.