A series of alkenes with bistable isomers were obtained containing a thiophene/azoheteroaryl backbone. Visible light and heat-induced reversible cis ⇌ trans isomerizations were evidenced by UV-Vis and 1H NMR spectra. The stabilization of cis alkenes was attributed to intramolecular sulphurπ (Sπ) interactions, which were further supported by theoretical calculations.