A facile method of preparing hierarchical hollow silica microspheres containing surface silica nanoparticles (HHSMs) through the sol gel process of tetraethylorthosilicate employing a quasi-hard template of non-cross-linking poly(4-vinylpyridine) microspheres is proposed. The quasi-hard template contains the inherent catalyst of the basic pyridine group, and a few of the polymer chains can escape from the template matrix into the aqueous phase, which initiates the sol gel process spontaneously both on the surface of the template used to prepare the hollow silica shell and in the aqueous phase to produce the surface silica nanoparticles. By tuning the weight ratio of the silica precursor to the quasi-hard template, HHSMs with a size of about 180 nm and a shell thickness ranging from 14 to 32 nm and surface silica nanoparticles ranging from 17 to 36 nm are produced initially through the deposition of surface silica nanoparticles onto the silica shell, followed by template removal either by calcination or solvent extraction. The synthesized HHSMs are characterized, and a possible mechanism for the synthesis of HHSMs is proposed.