To confirm the hierarchical porous structure of these two chiral macrocyclic POPs, their inherent pore structure and distribution were further investigated via the adsorption and desorption of N 2 (Figure and S20). The Brunauer-Emmett-Teller (BET) surface areas of PRBT and PSBT was recorded to be approximately 1007 m 2 g -1 and 992 m 2 g -1 , respectively. And the pore size distribution profiles for chiral POPs revealed the presence of micropores with a size of about 0.57 nm, 1.35 nm and 2.92 nm (Figure ), whereas the small cavity was attributed to the intrinsic pore of the CCMs and the larger voids were originated from the three-dimensional scaffold (Figure ). This multiple-modal pore size distribution directly con-firmed the hierarchical porous structures of PRBT and PSBT, in which the chiral voids within CCM unit had been well retained in chiral macrocyclic POPs.