A brief review of recent results from our efforts to elucidate the mechanistic details of the surface chemistry of hydrocarbons on transition metal surfaces will be presented. The chemistry of C4 hydrocarbons on Pt(111) single-crystal surfaces will be highlighted, with focus on the steps responsible for double bond migration and cis-trans isomerization in olefins. A comparison will be provided with our previous studies using shorter moieties, and the role of different key intermediates such as alkyls and allyls will be discussed. Insertion reactions will be addressed next. Specifically, the mechanism of chain growth on Ni(110) surfaces will be analyzed in terms of the chemistry of methylene and methyl on that surface. The effect of coadsorbed oxygen on these reactions, as well as the opening of new oxygen incorporation steps, will be discussed. Finally, reference will be made to the surface chemistry of chiral compounds on metals as it relates to enantioselective catalysis.