In this article, a comparative study of the preparation and physical properties of as‐prepared PMMA‐silica nano‐hybrid (PSN) and sub‐micro‐hybrid (PSM) latexes is successfully presented. Vinyl‐modified silica spheres were prepared using the Stöber process with/without a chelating agent to control particle size. The as‐prepared vinyl‐modified silica spheres with different particle sizes were subsequently characterized by SEM, 13C‐solid‐state NMR, and 29Si‐solid‐state NMR spectroscopy. A certain feeding amount of silica spheres was reacted with MMA monomers by emulsion polymerization to yield a series of PSN and corresponding PSM. Both as‐prepared nano/sub‐micronscale hybrid materials were further characterized by FTIR, SEM‐EDX mapping, and TEM studies. The comparative study on the physical properties of both as‐prepared nano/sub‐micron‐scale hybrid materials was done systematically based on a series of instrumentation evaluations performed using a dynamic mechanical analyzer, electrochemical corrosion measurements, salt spray test, and gas permeability analysis. Results indicated that PSN has more effectively enhanced mechanical properties, corrosion protection properties, as well as gas barrier compared to PSM. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers