Poly(ethyleneglycol dimethacrylate-co-methacrylic acid)@poly(ethyleneglycol-co-vinylpyridine)/titania/poly(N,N′-methylene bisacrylamide) (P(EGDMA-co-MAA)@P(EGDMA-co-VPy)/TiO2/PMBAAm) and P(EGDMA-co-MAAP)@P(EGDMA-co-VPy)/TiO2/poly(ethyleneglycol dimethacrylate) tetra-layer microspheres were synthesized by distillation precipitation polymerization of N,N′-methylene bisacrylamide (MBAAm) and ethyleneglycol dimethacrylate (EGDMA) in the presence of P(EGDMA-co-MAAP)@P(EGDMA-co-VPy)/TiO2 core-shell particles as the seeds in acetonitrile. The P(EGDMA-co-MAAP)@P(EGDMA-co-VPy)/TiO2 seeds were prepared by a combination of a two-stage distillation precipitation polymerization and the subsequently controlled hydrolysis of titanium tetrabutaoxide (TBOT) in ethanol–acetonitrile mixed solvents. The structures of the resultant polymer and polymer/titania, polymer/titania/polymer multi-layer composite microspheres were confirmed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FT-IR) and zeta-potential (ξ) analysis.