A simple and facile method for the synthesis of monodisperse microporous spherical silica particles is proposed. The method is based on a traditional Stöber technique with the use of ammonium metavanadate acting as a hard template for the micropore formation. The thus obtained silica particles possess an interconnected system of micropores that determines high values of their specific surface area (up to 320 m2 g-1) and pore volume (up to 0.25 cm3 g-1). The use of the Stöber method allows obtaining highly monodisperse spherical particles with the standard size deviation not exceeding 5%. The particles with an average diameter of 250 nm exhibit high sedimentation and aggregation stability and form stable hydrosol, which is important from the practical point of view.