Porous carbon is exceptionally useful, but it remains a great challenge to develop a facile route to prepare porous carbon materials with hierarchical structure and enhanced porosity. This work demonstrates a novel synthetic pathway for hierarchical carbonaceous materials (HCM) using isobutene and formaldehyde as carbon precursors via silica templates impregnated with phosphorus. Different from the traditional nanocasting method, the formation of the carbon structure is caused by heavy coke deposits on the solid catalyst in the course of the olefin/aldehyde vapor reaction. The coke-derived carbonaceous materials indicated by transmission electron microscopy (TEM) and nitrogen adsorption–desorption measurement are hierarchically mesoporous structures with a large surface area (971 m² g⁻¹) and pore volume (1.91 cm³ g⁻¹). We have demonstrated for the first time that the olefin/aldehyde reaction may provide a convenient route to develop a porous carbon texture. The newly developed method may lead to porous carbon having scientific and technological importance in adsorption and catalysis applications.