Solid vinyl monomer with functional group "phthalonitrile" was successfully introduced into microspheres to make poly{styene-co-4-(4-vinylphenoxy) phthalonitrile} microspheres (PSPMs) with uniform (UPSPMs) and core-shell (core-shell PSPMs) structure using soap-free emulsion polymerization by the new approach of "codissolution". The core-shell PSPMs then were used as the design platform to make metallophthalocyanine-containing microspheres. EA, FTIR, SEM, TEM, UV-vis, TGA, XPS, solid 1 H NMR and XRD techniques were employed to analyze the formation and morphology of PSPMs and metallophthalocyanine-containing microspheres. The results showed that UPSPMs and core-shell PSPMs were both realized and they were regular sphericities with diameters of around 370 nm. The percentages of reacting weight of 4-(4-vinylphenoxy) phthalonitrile were close to 50%. Based on the design platform of core-shell PSPMs, metallophthalocyanine-containing microspheres could be obtained and the content of metallophthalocyanine was close to 19%.
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