Covalent organic frameworks (COFs) are a class of crystalline porous materials utilized in various potential applications. However, the development of hollow-structured COFs with defined morphology is important for their further applications, which is rare. Herein, COF with unique hollow shuttle morphology was prepared by a Schiff condensation reaction between 4-(4-aldehyde phenyl)ethylene (TPE) and tetra-(4-aminophenyl) porphyrin (TAP). A detailed mechanistic investigation reveals that an initial self-assembly followed by a similar inside-out Ostwald ripening process is responsible for the hollow capsule formation. The hollow microshuttle-shaped capsule COF is used for studying hemoglobin adsorption, which shows an uptake of 550.82 mg g-1 of hemoglobin. These studies could foreshadow new avenues for the development of porous materials with defined morphologies for the adsorption of biomolecules.