The effect of the ZrO2 loading was studied on spherical SiO2@ZrO2-CaO structures synthetized by a simple route that combines the Stöber and sol-gel methods. The texture of these materials was determined using SBET by N2 adsorption, where the increment in SiO2 spheres' surface areas was reached with the incorporation of ZrO2. Combined the characterization techniques of using different alcoholic dissolutions of zirconium (VI) butoxide 0.04 M, 0.06 M, and 0.08 M, we obtained SiO2@ZrO2 materials with 5.7, 20.2, and 25.2 wt % of Zr. Transmission electron microscopy (TEM) analysis also uncovered the shape and reproducibility of the SiO2 spheres. The presence of Zr and Ca in the core-shell was also determined by TEM. X-ray diffraction (XRD) profiles showed that the c-ZrO2 phase changed in to m-ZrO2 by incorporating calcium, which was confirmed by Raman spectroscopy. The purity of the SiO2 spheres, as well as the presence of Zr and Ca in the core-shell, was assessed by the Fourier transform infrared (FTIR) method. CO2 temperature programmed desorption (TPD-CO2) measurements confirmed the increment in the amount of the basic sites and strength of these basic sites due to calcium incorporation. The catalyst reuse in FAME production from canola oil transesterification allowed confirmation that these calcium core@shell catalysts turn out to be actives and stables for this reaction.