Due to the unique microstructure and superior catalytic properties, organic-inorganic hybrid materials attract extensive attention. Herein, we report a facile coprecipitation method for the fabrication of metalloporphyrin-metal phosphate salt hybrid spheres, and the cycloaddition of carbon dioxide with epoxides is employed as probe reaction to evaluate the catalytic performance of our as-synthesized catalysts. The hybrid spheres composed of meso-tetra-(4-N-pyridyl) zinc porphyrin (ZnTPyP)magnesium phosphate exhibited superior catalytic performance, and the conversion was much higher than that of individual ZnTPyP and magnesium phosphate, probably because of the acid-base synergistic effect. Meanwhile, the spheres showed excellent stability during the circulation experiments as well as compatibility with a wide scope of substrates. This work provides a valuable approach for the preparation of novel and efficient heterogeneous catalytic composites.Organic-inorganic hybrid materials with hierarchical structures have attracted ever increasing attention due to their potential applications related to catalysis, adsorption, drug delivery, and energy storage. [1] Recently, an encouraging breakthrough in the synthesis of organic-inorganic hybrid materials derived from biomolecules emerged. Ge et al. reported a convenient and ecofriendly coprecipitation method to synthesize hybrid nanoflowers based on the combination of enzyme molecules with metal salts in phosphate buffer. [2] The as-obtained hybrid materials showed enhanced enzymatic activity as well as improved stability and reusability. With the extensive studies, bovine serum albumin, [3] papain, [4] glucoamylase, [5] laccase, [6] peroxidase, [7] and metalloporphyrins [8] were used as organic components, while copper phosphate, [9] manganese phosphate, [10] cobaltous phosphate, [3] zinc phosphate, [11] and calcium phosphate were employed as inorganic components. [12] And it should be noted that in many previous reports, the synergistic effects between organic and inorganic components were also observed. Comparing with the ordinary catalytic systems of individual components, the hybrid materials composed of organic and inorganic components showed remarkable enhancement in the catalytic activities. For example, the enzyme activity of the trypsin embedded nanoflowers, which was reported by Lin et al., was determined approximately 270% higher than free trypsin in solution. [13] The results showed that the dramatically enhanced activity of trypsin embedded hybrid nanoflowers can be attributed to the allosteric modulation. In addition, as reported by Wang et al.,