A variety of surface-sensitive techniques are used to elucidate the reaction pathways, as well as adsorbate structures, associated with thermal activation of CF3I following adsorption on Ru(001) at 100 K. XPS shows that the C-I bond of CF3I dissociates below 200 K to form CF3(ad) and I(ad); the subsequent reactions of CF3 are best viewed as being regulated by the availability of surface sites. CF3(ad) dissociates to CF2(ad) below 200 K. Further CF3 dissociation, some of which is activated by H(ad), occurs between 200 and 400 K until all available sites are filled. Desorption of the remaining CF3, peaking at 705 K, once again opens surface sites for decomposition. This is followed by recombination of the products to form CF3(g). No evidence for CF(ad) is ever observed. Hydrogen coadsorption studies explain interesting features associated with fluorine evolution. HREELS and ESDIAD results indicate that CF3 adopts a tilted configuration on Ru(001).