Multilayer microcapsules with a biconcave discoidal shape mimicking the red blood cells (RBCs) were fabricated by covalent assembly of polyallylamine on RBC-like Ca(OH)2 particles, followed by core removal. Their morphology was verified by scanning electron microscopy and confocal laser scanning microscopy. Deformation of the 6.7 μm RBC-like capsules after being trapped into a 5 μm micro-capillary took place at the contacting parts with the capillary. They showed elastic deformation after liberated from the constriction, resulting in a high recovery ratio of ~90%. These capsules also could be endowed with reversible oxygen binding-releasing capacity by assembly of hemoglobin (Hb).