The thermal desorption profiles of thiophene on Si(1 1 1)7 x 7 were obtained for room temperature exposure. Thiophene was found to desorb molecularly from the Si surface. Two bonding phases were found to exist for the room temperature adsorption. The effects of altering the surface using Ar+ ion bombardment and pre-exposure to oxygen were also investigated. With thiophene and oxygen coadsorbed on the 7 x 7 surface, the desorption profile indicated that the oxygen was capable of stabilizing the adsorbed thiophene. The results in the present work are compared with literature photoemission and HREELS data of a related system: thiophene on cleaved Si(1 1 1)2 x 1.