We developed a series of porous organic polymer (POP) supported chloramphenicol base (ANP) derived organocatalysts with different polymeric condition or molecule structure and applied it to the asymmetric alcoholysis of cyclic meso -anhydrides. The optimal POP catalyst shows great enantioselectivity and good recyclability in asymmetric organocatalysis, which are the best performance in the research of ANP catalysts for asymmetric desymmetrization of cyclic meso -anhydrides. [Display omitted] • Starting material for porous organic polymer (POP) catalyst—(1 S , 2 S)-2-amino-1-(p -nitrophenyl)propane-1, 3-diol, as a chiral waste in the industrial production of chloramphenicol, enables efficient use of waste to a great extent. • The optimal POP catalyst shows great catalytic performance and good recyclability in asymmetric desymmetrization of meso -cyclic anhydrides, which even surpasses the corresponding homogeneous counterparts. • Potential application of POP catalyst in the formal synthesis of (+)-grandisol and total synthesis of (S)-pregabalin and (S)-piperidone. • The POP catalysts could be recovered easily and reused multiple times (10 runs) without apparent loss of catalytic activity and enantioselectivity. A series of porous organic polymer (POP) supported chloramphenicol base (ANP) derived catalysts are designed and prepared. A deep study of the polymerization condition, including reaction temperature, the ratio of monomers and the option of polymetric position on ANP scaffold was conducted. The best catalyst, poly - I a, performs high stereoselectivity and catalytic activity (up to 98% yield and 99% ee) in asymmetric alcoholysis of meso -cyclic anhydride with the possibility of high recyclability (at least 10 times). More importantly, poly - I a even obtains higher enantioselectivity compared to its homogeneous monomer, which overcomes the common drawback of heterogeneous organocatalysts, for instance, lower selectivity and diminished reactivity. [ABSTRACT FROM AUTHOR]