The surface of nanodent and nanopore structured alumina membranes with different periods were directly modified by Angelica sinensis polysaccharide (ASP) or covalently modified by ASP via γ-aminopropyl triethoxysilane (KH550). After that, the morphology and cell viability of breast cancer cells MDA-MB-231 grew on the modified nanostructured surfaces were systematically studied. It was found that nanodent and nanopore structure directly modified by ASP could effectively inhibit the viability of breast cancer cells, and had little effect on cell morphology. However, the inhibitory effect of nanodent structure on cell viability was superior to that of nanopore structure. Nanodent structure with period of 300 nm had the best inhibitory effect on cell viability, and the inhibitory rate is 27.7%. The nanodent and nanopore structures covalently modified by ASP via KH550 had a better inhibitory effect on cell viability than that directly modified ASP, and the cell morphology changed obviously. A large number of lamellipodia were generated around the cell body. However, the inhibition effect of the nanodent structure on cell viability was better than that of the nanopore structure. Nanodent structure with period of 300 nm had the best inhibitory effect, and the inhibition rate is 28.2%. These results have a certain function for the design and delivery of drugs.