A hydrogen-terminated Si(111) surface has been covalently modified by UV irradiation in the presence of ethyl undecylenate leading to a Si(111)-C10H20CO2Et surface. It is possible to carry out a diverse range of chemical manipulations of the ester group on the surface. For example, reduction with sodium borohydride provides a surface terminated with a primary alcohol. Reaction with an alkyl Grignard reagent gives a tertiary alcohol that can be acylated with acetyl chloride. Finally, hydrolysis of the ester leads to a carboxylic acid terminated surface that can be coupled to an amino acid using a standard solid phase amide coupling protocol. The surface density of the ester function can be controlled by dilution of the reacting ester with a long-chain alkene. This has the beneficial effects of minimizing the disruption of the alkyl chain packing in the monolayers and avoiding steric blocking of the ester group. It is expected that the ability to precisely control the average distance between large biomolecules on surfaces will impact on future molecular electronic, sensor, and biochip technologies.