A series of carboxylic acid functionalized hybrid linear-dendritic block copolymers (LDBCs) derived from methoxy poly(ethylene glycol) (MPEG) and variant generation dendrons from 2,2-bis(hydroxymethyl) propionic acid were synthesized and employed as CaCO3 crystallization growth modifiers. Mainly spherical vaterite particles of gradually reduced sizes were produced with the increase of the polymer additive concentration and/or the dendron segment generation number, while the incorporated polymer organic components in the particles increased for the promoted binding efficiency and ever enhanced adsorption ability. A higher mineralization temperature resulted in significantly larger particle size and partly calcite formation. Under the same molar concentration of carboxylic acid, the same size level particles were obtained which manifested the crucial role of the functional group, meanwhile, the slight decrease of the spherical vaterite diameters with increasing generation number and especially the formation of particular pine-cone shaped calcite crystals also revealed the significant effect of the architectural structure of variant generations and some special characters of the hybrid LDBC structures. (c) 2008 Elsevier Ltd. All rights reserved.