Block copolymer assembled colloidal particles were successfully prepared through electrostatic interactions between cationic polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) and anionic polystyrene-block-poly(acrylic acid) (PS-b-PAA) in a one-pot process The colloidal particles were prepared by simple mixing of complementary charged block copolymer micelle aqueous solution This process presents the possibility of very simple and versatile method of mass production of BCM based colloidal particles Both hairy and crew-cut types of block copolymer micelles (BCMs) showed different electrostatic assembly tendencies as confirmed by Field emission scanning electron microscopy (FE SEM) These phenomena are mainly caused by the different degrees of electrostatic interdigitation and entanglement between the protonated and deprotonated corona block regions of the micelles (C) 2010 Elsevier B V All rights reserved