In this paper, Fe (III), Zn (II), and Cr (III) were used to complex with corn silk polysaccharide (CSP) by classical methods and CSP-Fe, CSP-Zn, and CSP-Cr were successfully synthesized, respectively. The physicochemical properties and structural features were characterized by chemical composition analysis, inductive coupled plasma-mass spectrometry (ICP-MS), ultraviolet-visible (UV–Vis) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, fourier transform infrared (FT-IR) spectroscopy, circular dichroism (CD) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and differential scanning calorimetry (DSC), respectively. The antioxidant activities and inhibitory effects on α-glucosidase of CSP, CSP-Fe, CSP-Zn, and CSP-Cr were compared. The results showed that the Fe (III), Zn (II), and Cr (III) chelation could change the morphology, conformation, thermostability, and biological activities of CSP. CSP-Zn exhibited higher antioxidant activities and inhibition effects on α-glucosidase than CSP, which suggested that it could be considered as a potential candidate for developing an ingredient of functional foods for antidiabetics.