Hollow calcium carbonate(CaCO3) microspheres with different morphologies were synthesized via the precipitation reaction of calcium chloride with sodium carbonate in the presence of different surfactant-polymer complexes.The selected anionic surfactants were sodium dodecyl sulfonate(SDS) and sodium dodecyl benzenesulfonate(SDBS),respectively.The selected water-soluble polymers were polyacrylic acid(PAA) and polyvinyl pyrrolidone(PVP).In this work,SDS-PVP “pearl-necklace model” micellar complex was formed via hydrophobic effectiveness between SDS and PVP and it served as the spherical template to generate spherical CaCO3 aggregates with hollow microspheres composed of about 500 nm irregular shaped particles.SDS-PAA complexes and SDBS-PAA complexes formed “core-shell model” aggregates with calcium ions serving as the medium to link the anionic surfactant and the polymer.SDS-PAA “core-shell model” aggregates would act as templates for hollow CaCO3 microspheres consisting of 30―50 nm irregular shaped crystallites.SDBS-PAA “core-shell model” aggregates served as the spherical aggregate templates to generate spherical CaCO3 aggregates consisted of many small spherical particles which had grown together.All the obtained CaCO3 hollow microspheres are calcite particles.This research may provide new insight into the control of morphologies of hollow CaCO3 microspheres in the presence of surfactantpolymer complexes. Hollow calcium carbonate (CaCO3) microspheres with different morphologies were synthesized via the precipitation reaction of calcium chloride with sodium carbonate in the presence of different surfactant-polymer complexes. The selected anionic surfactants were sodium dodecyl sulfonate (SDS) and sodium dodecyl benzenesulfonate (SDBS) , respectively.The selected water-soluble polymers were polyacrylic acid (PAA) and polyvinyl pyrrolidone (PVP) .In this work, SDS-PVP “pearl-necklace model” micellar complex was formed via hydrophobic effectiveness between SDS and PVP and it served as the spherical template to generate spherical CaCO3 aggregates with hollow microspheres composed of about 500 nm irregular shaped particles. SDS-PAA complexes and SDBS-PAA complexes formed “core-shell model ” aggregates with calcium ions serving as the medium to link the anionic surfactant and the polymer. SDS-PAA “core-shell model” aggregates would act as templates for hollow CaCO3 microspheres consisting of 30-50 nm irregular shaped crystallites. SDBS-PAA “core-shell model ” aggregates served as the spherical aggregate templates to generate spherical CaCO3 aggregates consisted of many small spherical particles which had grown together. All the obtained CaCO3 hollow microspheres are calcite particles. research may provide new insight into the control of morphologies of hollow CaCO3 microspheres in the presence of surfactant polymer complexes.