Novel porous poly(methyl methacrylate) (PMMA) silica nanocomposites have been produced by utilization of polymerization-induced phase separation in a simple one-pot approach. A facile free radical polymerization of MMA in the presence of surface methacrylate-functionalized silica nanoparticles was carried out in ethanol-based solvents, successfully producing novel, morphologically designable porous nanocomposite monoliths. Differing from standard free radical polymerization in solution, a mixture of good and poor solvents (ethanol/N,N-dimethylformamide ratio) for the resulting polymer was used to trigger spinodal phase separation. The influence of monomer concentration, as well as solvent composition, on the morphology of the resulting porous polymers has been investigated. Porous monolith structures composed of connected particles and co-continuous morphologies were observed under a scanning electron microscope depending on the polymerization conditions. The resulting polymers were insoluble and showed swelling characteristics in some organic solvents that are capable of dissolving regular PMMA, indicating covalent bonds between the functionalized silica nanoparticles and the polymer chains. The presence of silica particles in the final polymer was proven via an ATR-IR analysis. The glass transition temperature of the present PMMA−silica nanocomposite was higher than that of the conventional PMMA. The porous polymer immersed in a mixed organic solvent showed coloration induced by the Christiansen effect.