We report the synthesis of polyelectrolyte-decorated hybrid colloidal particles by using negatively charged polyelectrolyte complex (PEC) micelles as colloidal templates for silica mineralization under ambient conditions. The negatively charged polyelectrolytes including poly(acrylic acid) (PAA), poly(L-glutamic acid) (PLGA), and poly(styrene sulfonate) (PSS) were complexed with poly(L-lysine) at non-stoichiometric mixing weight percentage to form negatively charged PEC micelles. Varying the mixing weight percentage and molecular weight of polyelectrolytes led to the changes in the size and charge of the PEC particles. Silica mineralization in the complex core resulted in the colloidally stable hybrid particles decorated with different negatively charged polyelectrolytes. The colloidal properties of these polyelectrolyte-decorated hybrid particles were determined by the composition and decorated polyelectrolyte. This approach provided a simple and facile method to prepare polymer-decorated hybrid colloidal particles comprised of different polymers and their colloidal properties can be easily tuned by varying the decorated polymer and synthesis condition. (C) 2014 Elsevier Inc. All rights reserved.