Block copolymers (BCPs) have been intensively used as structure-directing agents for the synthesis of mesostructured materials because of their rich microphase separation and excellent thermal stability. Incorporating functional moieties into BCPs to extend the currently dominated monotonic role may open new opportunities in the creation of mesostructured materials using one single BCP system. In this work, we reported a new kind of pyrrole-containing BCP (PPHMA-b-PEO), finding that PPHMA-b-PEO could produce the effect of killing more birds with one stone and efficient fabrication of diverse mesostructured materials could be facilely realized. As a structure-directing agent, different ordered mesoporous silicas were produced as expected by using PPHMA-b-PEO. Importantly, the pyrrole-containing template molecules (PPHMA-b-PEO) confined in silica channels could also be used as a polymerizable monomer or precursor for further chemical transformation, leading to a mesostructured polymer and carbon materials. Moreover, because of the reductive activity of pyrrole, numerous oxidative agents could be explored to carry out the related polymerization process, making it possible to facilely access the diverse-doped mesostructured polymer or carbon materials. In addition to mesostructured silica, polymer, and carbon materials, it is also found that the uniform carbon coating derived from PPHMA-b-PEO could serve as a robust support for realizing the mesoporous metal oxides with high crystallinity, as demonstrated by the formation of high crystalline TiO2. All of our results indicate that the rational incorporation of functional moieties into BCPs will bring new opportunities and show great potential for the efficient fabrication of diverse mesostructured materials.