This paper aims to solve the problem of the reversibility in carbonation/calcination cycles of Ca-based materials. The CaO/CaZrO3 hollow sphere sorbents were prepared using colloidal carbon spheres as a template via the co-adsorption method. The hollow structure sorbents, which contained two kinds of metal ions, were observed by scanning electron microscopy and transmission electron microscopy images, and the components were obtained by X-ray diffraction and energy dispersive X-ray analysis. The performances in CO2 capture at different absorption temperatures, calcination temperatures, molar ratios of Ca/Zr, and heating rates compared to calcium oxide were investigated employing the thermogravimetric analyzer. The results showed that the CaO/CaZrO3 sorbent could be fabricated using a trace Zr precursor and the specific prepared sorbent still could maintain a high capture capacity after exceeding a 12 000 min operation, which suggesting the approach that adsorbs both calcium and zirconium ions on the colloidal carbon spheres to form a hollow structure is feasible for enhancing the sintering-resistant properties.