In this work, we reported the preparation and chemical analysis of novel polyhedral oligomeric silsesquioxane (POSS)-based porous materials, which were prepared according to Friedel-Crafts chloromethylation by using aluminum chloride as the catalyst and dichloromethane as the solvent. Through controlling the treatment solvent (water or methanol) and kinds of POSS, several materials with different morphologies were conveniently obtained. The chemical structure of porous materials was systematically characterized by Fourier-transform infrared (FTIR) spectra, 29Si Nuclear Magnetic Resonance (NMR), 13C NMR, and X-ray photoelectron spectroscopy (XPS). The samples were further characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA) to study their crystallinity, morphology, and thermal properties, respectively. The work systematically demonstrated the chemical structure of the porous materials. Moreover, the advantages and disadvantages of the preparation method and typical properties of the material were evaluated through a comparative analysis with other related research works.