To improve the near-infrared (NIR) solar reflectance of ZnSxSe1-x or copper-/indium-co-doped ZnSxSe1-x (ZnSxSe1-x:Cu/In) pigment with various colors, hollow glass microspheres (HGMs)@ZnSxSe1-x or ZnSxSe1-x:Cu/In composite pigments with a litchis-like core-shell structure were prepared with HGMs dispersed and surface-corroded in an alkali-solution under ultrasound and ZnSxSe1-x or ZnSxSe1-x:Cu/In particles deposited on HGMs surface via in-situ co-precipitation and subsequent sintering. The structure, particle size, morphology, color properties and thermal performance of the composite pigments were investigated by X-ray diffraction (XRD), Fourier transfer infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), laser diffraction particle size analysis, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), nitrogen gas adsorption method (BET), ultraviolet-visible-near-infrared (UV-VIS-NIR) spectroscopy and infrared irradiation image analysis. The results show that ultrasound can promote the corrosion of HGMs surface in alkali solution and form a mesh-pore structure, thus providing some heterogeneous nucleation sites on HGMs surface and favoring the nucleation of pigment precursors on HGMs surface in subsequent in-situ co-precipitation reaction. Compared to ZnSxSe1-x or ZnSxSe1-x:Cu/In pigments, HGMs@ZnSxSe1-x or ZnSxSe1-x:Cu/In composite pigments have a higher solar reflectance since the multiple layer reflections occur at the interface between the pigment particles and HGMs, thus leading to a better heat-reflective property. The NIR solar reflectance of HGMs@ZnSxSe1-x or ZnSxSe1-x:Cu/In composite pigments is 90.61 +/- 0.052% or 73.13 +/- 0.046%. The surface temperature of aluminum plate coated with HGMs@ZnSxSe1-x composite yellow pigment is 3.4 +/- 0.2 degrees C or 9.6 +/- 0.2 degrees C lower than that of aluminum plate coated or uncoated with ZnS..Sei pigment. This approach may shed a light on a promising composite structure design for high-performance solar reflective 'cool materials'.