In　this　review,　the　organic　cycloaddition　and　complexation　of　transition　metal　oxides　with　alkene,　diamond　(100),　fullerene　and　carbon　nanotube　have　been　summarized.　A　clear　scenario　that　analogous　chemistry　reaction　is　able　to　occur　in　materials　featuring　an　analogous　bonding　motif　has　been　obtained.　In　particular,　it　is　demonstrated　that　theoretical　predictions　can　be　employed　as　a　very　useful　tool　to　provide　experiments　with　potentially　guided　information.　RuO4　is　proposed　to　be　a　better　candidate　than　OsO4　for　investigating　the　cycloaddition　of　transition　metal　oxides　with　fullerene　and　carbon　nanotube.　In　perspective,　the　typical　organic　cycloaddition　and　complexation　of　transition　metal　oxides　with　alkenes　in　organic　chemistry　could　be　extended　to　functionalize　other　structure-like　substances　including　Si　(100),　Ge　(100),　disilene,　digermene,　silene　and　germene.　©　2008　Bentham　Science　Publishers　Ltd.