Layered organic polymer nanocomposites were developed utilizing supercritical fluid technology and solid-state polymerization. Intimately mixed composite particles consisting of one amorphous and one crystalline component were precipitated by the method known as rapid expansion of supercritical solutions (RESS). The crystalline component was 2,5-distyrylpyrazine (DSP), a diolefinic monomer with solid-state reactivity. The amorphous component was a fluoroalkyl acrylate (FAA) polymer. The DSP monomer, though normally highly crystalline, was rapidly precipitated in a nonequilibrium state and recrystallized and polymerized in the solid state. The process of DSP monomer reorganization within the organic polymer matrix resulted in the formation of well-organized alternating nanoscale layers of DSP and FAA phases throughout the particle volume.