Bovine serum albumin (BSA) is a familiar protein and often used as a model drug to test the adsorption efficiency of material, while the cytotoxicity of hybrid is overlooked. In this study, we synthesized hierarchical mesoporous flower-like Mg–Al layered double hydroxide (LDH) microspheres through anion surfactant mediated hydrothermal method. The scanning electron microscopic images demonstrated that 10S-LDH and 100S-LDH samples possessed a porous surface and the porosity structure were affected by the concentration of anionic surfactant, i.e., sodium dodecyl sulfonate (SDS). By being immersed in the BSA/phosphate buffer solution (PBS) solution, the 100S-LDH had a loading capacity about 44.6 mg/g. Compared to 1S-LDH and 10S-LDH, the SDS intercalated in 100S-LDH could form the hydrogen bond with BSA molecules and promote the adsorption efficiency. In the cytotoxicity test towards Raw264.7 cells, the hybrid of BSA and [Formula: see text]S-LDH showed a superior biocompatibility to the raw LDH materials. The SDS intercalated Mg–Al LDH is expected to be used in the bioactive molecules delivery.