High-resolution scanning tunneling microscopy has been used to investigate the adsorption of a variety of unsaturated organic molecules on the (001) surface of silicon and germanium. Results are presented for a number of prototypical alkenes, conjugated and non-conjugated dienes, and aromatic compounds. These include cyclopentene, 1,5-cyclooctadiene, norbornadiene, 2,3-dimethyl-1,3-butadiene, and benzene on the Si(001) surface, and for cyclopentene on the Ge(001) surface. Factors controlling the selectivity of various reaction pathways and the consequences for preparation of ordered organic overlayers are discussed.