Heterogeneous asymmetric multicomponent/multicatalytic organocascade faces the enormous challenges of tedious immobilization of catalysts, mass transfer, and stereoselective control. In this paper, the mesopore-abundant and well-shaped hollow mesoporous organic polymers, nano bowls (HMOPBs) and nanospheres (HMOPSs), are fabricated via emulsion polymerization of styrene on a polystyrene (PS) core and then removal of PS, accompanied by the adsorption of Co2+ ions, transformation of Co2+ into Co(OH)(2), and final removal of Co(OH)(2). Among them, the nanobowl HMOPBs(a) with hollow interiors, mesoporous shells, and thin shell thickness (16 nm) possesses the largest surface area (185.7 m(2) g(-1)) and displays the highest reaction kinetics in the sulfonation (2.85 mmol H+ g(-1)) and then immobilization of 9-amino(9-deoxy)epi-quinine (QNNH(2), 1.35 mmol g(-1)). For the 2,4-substituted bulky reactants in an asymmetric double-Michael cascade, the as-fabricated functional nanobowl can provide a suitable microenvironment to meet the requirements of the good to excellent double-Michael organocascades, which originates from its thin shell thickness and mesopore-dependent shell.