CaCO3 crystals with different hierarchical structure were fabricated by the precipitation of CaCO3 in an aqueous solution containing guar gum (GG). Through adjusting a range of parameters, the size distribution and microstructure of CaCO3 were well controlled. Results showed that GG facilitated the formation of the hierarchical hollow sphere through assembling of nanocrystals, while inhibited the growth of CaCO3 crystals and restrained phase transition from calcite to vaterite at high concentration of GG (CGG) condition; Moreover, increasing reaction temperature led to larger particles and stable crystalline phase formed. According to the results, a morphology map was presented. Furthermore, Drug loading and releasing results ensured porous CaCO3 microspheres a promising vector for drug delivery.