Copyright © 2019 American Chemical Society. The mechanical properties of microparticles intended for in vivo applications as drug delivery vehicles are among important parameters that influence their circulation in the blood and govern particle biodistribution. We report on the synthesis of soft but mechanically robust spherical capsules via a hydrogen-bonded multilayer assembly of (poly(N-vinylpyrrolidone), Mw = 10000 g mol-1) with (poly(methacrylic acid) Mw = 100000 g mol-1)) (PVPON/PMAA)n in methanol using 4 μm nonporous silica microparticles as sacrificial templates, where n = 5 and 10 and represents the bilayer number. The mechanical properties of (PVPON/PMAA)n spherical capsules were assessed using the osmotic pressure difference method and resulted in an elasticity modulus of 97 ± 8 MPa, which is in the range of Young's modulus for elastomeric networks. We also found that hydrogen-bonded (PVPON/PMAA)10 capsules demonstrated almost complete recovery from a concave buckled inward shape induced by the osmotic pressure difference from the addition of polystyrene sulfonate (PSS) to the capsule solution to their initial spherical shape within 12 h after the PSS solution was rinsed off. The permeability measurements through the capsule shell using fluorescently labeled dextran molecular probes revealed that the average mesh size of the hydrogen-bonded network assembled in methanol is in the range of 3 to 9 nm and is not permeable to FITC-dextran with a molecular weight of >40000 g mol-1. Our study shows that physically cross-linked polyelectrolyte multilayer capsules are capable of withstanding large deformations, which is essential to the development of adaptable particles for controlled delivery.