We demonstrate a new method to switch on and off the rotational motion of a long-chain molecule by controlling the bonding geometry between the molecule and a substrate. An azobenzene derivative molecule adsorbed on a Au(111) surface is immobile only when its three rotation centers, comprised of two phenyl rings and a nitrogen-nitrogen bond, are located at hollow sites of the Au(111) surface, as observed by scanning tunneling microscopy. Rotational motion can be activated by exciting the vibrational modes and inducing hopping motion away from the immobile site with a voltage pulse.