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.