In this study, the complexation ability of HG-type hawthorn pectin with trivalent iron ions after de-esterification was investigated. The moderate esterification reaction could significantly increase the iron content in HG-type hawthorn pectin. Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) experiments proved that -OH and -COOH in the pectin acted as a bridge connecting Fe3+ leading to the formation of β-FeOOH structure, and the trivalent iron ions were successfully complexed into the HG-type hawthorn pectin. In addition, infrared and ultraviolet spectroscopic scans, particle size, and potentiometric measurements were carried out to demonstrate the complexation coordination mechanism of hawthorn pectin with Fe3+, and there were differences in the complexation effect of HG-type hawthorn pectin with different degrees of esterification. The gelling properties of HG-type hawthorn pectin were subsequently verified by in vitro gastrointestinal tract simulation experiments to aid the smooth passage of ferric ions through the gastric juices and reduce irritation. The success of the experiments demonstrated that HG-type hawthorn pectin is an excellent raw material for metal complexation, and the degree of esterification is one of the important factors affecting its complexation effect, which proves its potential application value as an iron supplement.