Mass transfer limitation and tedious anchoring of multiple expensive chiral organocatalysts are the key bottlenecks in heterogeneous asymmetric cascade/tandem reactions, leading to high-cost processes with low catalytic performances. In this paper, two chiral organocatalysts, including (S)-diphenylprolinoltrimethylsilyl ether (ProTMS) and N-heterocyclic carbenes (NHC), are simultaneously immobilized to hollow mesoporous polystyrene nanospheres (HMPNs) in one-pot via Friedel-Crafts alkylation to afford supported dual organocatalysts (ProTMS&NHC@HMPNs) at low cost. The catalyst possesses the spherical morphology with a hollow interior and a thin mesopore-abundant shell, providing suitable environments for reactants to quickly access to the catalytic sites of NHC and ProTMS. The side reactions caused by limited mass transfer are effectively suppressed, and superior yields (70–92 %) and diastereoselectivities (dr = 3:120:1) to homogeneous catalysis are achieved in heterogeneous Michael/benzoin cascade reaction. Overall, the mass transfer-enhanced platform for efficient heterogeneous dual organocatalysis is developed to boost yield and diastereoselectivity in asymmetric cascade reactions.