Self‐assembled monolayers (SAMs) of N‐heterocyclic olefins (NHOs) have been prepared on Au (111) and their thermal stability, adsorption geometry, molecular order were characterized by X‐ray photoelectron spectroscopy, polarized absorption scanning tunneling microscopy (STM), density functional theory (DFT) calculations. The strong σ‐bond character NHO anchoring to induced high geometrical flex...