Nearly monodispersed silica-poly(methacrylic acid) (SiO2-PMAA) core-shell microspheres were synthesized by distillation-precipitation polymerization from 3-(trimethoxysilyl)propylmethacrylate-silica (SiO2-MPS) particle templates. SiO2-PMAA-SiO2 trilayer hybrid microspheres were subsequently prepared by coating of an outer layer Of SiO2 on the SiO2-PMAA core-shell microspheres in a sol-gel process. pH-Responsive PMAA hollow microspheres with flexible (deformable) shells were obtained after selective removal of the inorganic SiO2 core from the. SiO2-PMAA core-shell microspheres by HF etching. The pH-responsive properties of the PMAA hollow microspheres were investigated by dynamic laser scattering (DLS). On the other hand, concentric and rigid hollow silica microspheres were prepared by selective removal of the PMAA interlayer from the SiO2-PMAA-SiO2 trilayer hybrid microspheres during calcination. The hybrid composite microspheres, pH-sensitive hollow microspheres, and concentric hollow silica microspheres were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and energy-dispersive X-ray (EDX) analysis.