Self-assembly of photoresponsive molecules is a robust technology for reversibly tuning the chemical and electronic properties of functional materials. In most systems the photoactive group is separated from the surface by a spacer and thus the photo-responsiveness does not benefit from interactions with the metal. Herein, the impact of metal photoactive-group interactions on photoswitchability and surface potential were probed by self-assembly of N-heterocyclic carbene molecules (NHCs) that were functionalized with stilbene group directly on their imidazole ring. Stilbene-NHCs that were adsorbed on weakly interacting Au surface accumulated a vertical orientation, as identified by FTIR measurements. This positioning enabled structural flexibility and high photoisomerization efficiency that induced reversible changes in surface potential. Stilbene-NHCs that were anchored on Pt film accumulated flat-lying adsorption geometry due to strong metal-adsorbate interactions. These interactions limited the structural flexibility of the stilbene groups and induced deteriorated photoswitchability that led to lower photoinduced changes in surface potential. While stronger metal-adsorbate interactions hindered the photo-induced isomerization yield of stilbene, these interactions prompted the cis-to-trans thermal-induced isomerization rate, which was an order of magnitude higher on Pt than on Au.