Summary: In this paper two new donor‐embedded polybinaphthalenes prepared by the Heck reaction are presented. By introducing a double bond in the polymer backbone, the supramolecular structure was altered in comparison with polymers without the double bond. Comparison between the CD/UV‐Vis spectra of polymers, with and without the double bond (previously synthesized in our laboratory) proved this change in a supramolecular structure. The double bonds also allow crosslinking upon heat treatment. NLO experiments demonstrated a more stable nonlinearity over time depending on the degree of crosslinking.
