Polysaccharide materials have wide applications in the field of chiral recognition. Herein, a new series of chiral materials based on chiral polysaccharide were synthesized for electrochemical enantioselective recognition of tryptophan (Trp) enantiomers. Chiral recognition was investigated via differential pulse voltammetry (DPV). Among poly (L‐lactide) La/hydroxyapatite chitosan (PLLHC‐X) series materials (PLLHC‐0, PLLHC‐1, PLLHC‐3, PLLHC‐7 PLLHC‐9 and PLLHC‐5), PLLHC‐5 has the best recognition efficiency. And the results reveal that the PLLHC‐5 displays a stronger interaction with L‐Trp than to that of D‐Trp. The synergetic effect of chiral recognition from chitosan and signal amplification from poly (L‐la