Hierarchically porous biocompatible Mg-Al-Cl type LDH composites containing aluminum hydroxide (Alhy) have been prepared using a phase-separation process. The sol-gel synthesis allows for the hierarchical pores of the LDH-Alhy composites to be tuned, leading to a high specific solid surface area per unit volume available for high molecular weight protein adsorptions. A linear relationship between effective surface area, SEFF, and loading capacity of a model protein, bovine serum albumin (BSA) is established following successful control of the structure of the LDH-Alhy composite. The threshold of mean pore diameter, Dpm, above which BSA is effectively adsorbed on the surface of LDH-Alhy composites, is deduced as 20 nm. In particular, LDH-Alhy composite aerogels obtained via supercritical drying exhibits extremely high capacity for protein loading (996 mg/g) due to a large mean mesopore diameter (> 30 nm). The protein loading on LDH-Alhy is >14 times that of a reference LDH material (70 mg/g) prepared via a standard procedure. Importantly, BSA molecules pre-adsorbed on porous composites were successfully released on soaking in ionic solutions (HPO42− and Cl− aq.). The superior capability of the biocompatible LDH materials for loading, encapsulation, and releasing large quantity of proteins was clearly demonstrated, which potential uses in separation and purification in addition to a high-capacity storage medium.The present work is supported by JSPS-MAE SAKURA program (N°34148TB).The present work is partially supported by JSPS KAKENHI, and by a research grant from the Foundation for the Promotion of Ion Engineering