Herein we report a two-step tandem synthesis of hyper-cross-linking hollow microporous organic nanospheres (H-MONs) based on incorporation of reversible addition-fragmentation chain transfer (RAFT) polymerization and in-situ hyper-cross-linking self-assembly process in one-pot. The synthesized polylactide-b-polystyrene (PLA-b-PS) diblock copolymers and unreacted styrene (S) monomers, without further separation and purification after RAFT polymerization, are subsequently used to prepare H-MONs via a Fridel-Crafts reaction. The introduction of unreacted S monomer, which can act as a hyper-crosslinking monomer, leads to an obvious increase of the Brunauer-Emmett-Teller (BET) surface area with a large-scale production. More importantly, this strategy can be expanded to produce heteroatom-doped H-MONs by introducing functional building monomer. Moreover, the obtained H-MONs (H-MONs-24-S and H-MONs-24-N) exhibit an excellent adsorption performance toward poisonous pollutants, such as phenol and iodine. The proposed tandem strategy may provide a cost-effective method for producing novel hollow microporous organic nanospheres for various advanced applications in the future. (C) 2018 Elsevier Ltd. All rights reserved.