A very simple cooperative template-directed coating method is developed for the preparation of core-shell, hollow, and yolk-shell microporous carbon nanocomposites. Particularly, the cationic surfactant C16TMA(+)·Br(-) used in the coating procedure improves the core dispersion in the reaction media and serves as the soft template for mesostructured resorcinol-formaldehyde resin formation, which results in the uniform polymer and microporous carbon shell coating on most functional cores with different surface properties. The core diameter and the shell thickness of the nanocomposites can be precisely tailored. This approach is highly reproducible and scalable. Several grams of polymer and carbon nanocomposites can be easily prepared by a facile one-pot reaction. The Au@hydrophobic microporous carbon yolk-shell catalyst favors the reduction of more hydrophobic nitrobenzene than hydrophilic 4-nitrophenol by sodium borohydride, which makes this type of catalyst@carbon yolk-shell composites promising nanomaterials as selective catalysts for hydrophobic reactants.