This paper describes the chemical functionalization of hydrogen-terminated porous silicon surfaces with simple and functional 1-alkenes under microwave irradiation to give organic monolayers covalently attached to the surface through Si-C bonds. Using microwaves as a source of energy led to a remarkable increase in the rate of the hydrosilylation reaction and a higher surface coverage. This technique yields highly stable organic monolayers and allows the introduction of different functional groups on the surface (acid and ester) required for immobilization of more complex structures on the surface.