Based on the unique advantages including hollow interior, mesoporous shell, well-defined morphology and good compatibility with organic reactants, the first controllable fabrication of hollow mesoporous organic polymeric nanospheres (HMOPs) with pure intriguing mesopores was developed using low-cost and commonly available materials via metal ion adsorption in outer shell, in-situ forming metal hydroxide or phosphate expansion and removal of templates. After being sulfonated by ClSO3H, the resulting Co(OH)(2)-templated HMOPs with the highest acid exchange capacity (2.67 mmol g(-1)) could effectively immobilize versatile 9-amino(9- deoxy)epicinchonidine organocatalyst (0.98 mmol g(-1)) via acid-base interaction without multi-step chemical modification. In the green asymmetric aldol addition and double-Michael organocascade reaction, the mesoporeabundant HMOPs exhibited significantly higher catalytic performances in yields, diastereoselectivities and enantioselectivities than mesopore-deficient HNs due to the ordered mesoporous (2-15 nm), amphipathic shell and hollow interior. Based on the unchanged spherical morphology and hollow mesoporous structure, HMOPs was proved to possess a good mechanical stability in recycled processes.