The size of porous spherical calcium carbonate particles obtained by precipitation from a supersaturated solution has been controlled using bovine serum albumin as an organic additive and ethylene glycol and glycerol as cosolvents of the reaction mixture. The structural aspects of the formation of these particles, which affect the possibility of controlling their sizes, are considered. Highly porous vaterite particles with an average size of about 500 nm have been obtained by adding ethylene glycol and glycerol to the reaction mixture and agitation for no less than 30 min. It is shown that particles are formed as a result of the attachment of vaterite nanocrystallites, the shape of which is anisotropic and can be described by a biaxial ellipsoid.