Self‐supporting, interconnected, porous inorganic (silicon/carbon) membranes were obtained by the calcination of composite membranes at 900 °C with a porous polymer template obtained by binary‐phase solid‐state photopolymerization at −60 °C with acrylate monomers followed by chemical vapor deposition. The physicochemical properties of all of the membranes were characterized by scanning electron microscopy, energy‐dispersive spectroscopy (EDS), Fourier transform infrared (FTIR) spectroscopy, X‐ray powder diffraction (XRD), thermogravimetric analysis (TGA), and the measurement of water contact angles, water uptake, and percentage of porosity. The membranes showed contact angles ranging from 127 to 130 ± 0.5°, which were close to those of superhydrophobicity. The EDS, FTIR spectroscopy, XRD, and TGA results confirmed the formation of the Si–C composite structure after calcination and an increase in the thermal stability. The polymer and composite membranes were found to be hydrophilic, whereas Si–C was hydrophobic. The poly(ethylene glycol) diacrylate derived Si–C membrane showed a good absorption efficiency for tinted toluene from water compared to the others. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45822.