Nanoporous silica films were prepared through the templating of amphiphilic block copolymer, poly(styrene-2-vinyl pyridine) (PS-b-P2VP), and monodispersed colloidal silica nanoparticles. The experimental and theoretical studies suggested that the intermolecular hydrogen bonding existes between the colloidal silica nanoparticles and PS-b-P2VP. The effects of the loading ratio and P2VP chain length on the morphology and properties of the prepared nanoporous silica films were investigated. TEM and AFM studies showed that the uniform pore size could be achieved and the pore size increased with increasing porogen loading. The refractive index and dielectric constant of the prepared nanoporous films decreased with an increase in PS-b-P2VP loading. On the other hand, the porosity increased with an increasing PS-b-P2VP loading. This study demonstrated a methodology to control pore morphology and properties of the nanoporous silica films through the templating of PS-b-P2VP.