Developing a 3D material to support α-Fe2O3 nanorods to improve their adsorption performance for Congo Red (CR) is a major challenge. Herein, a novel 3D composite adsorbent was designed, where 2D material Ti3C2 MX and CoFe-LDH stacked on top of each other as the support material of α-Fe2O3 nanorods (α-Fe2O3@LDH@MX). The specific surface area of the α-Fe2O3@LDH@MX was increased by 2 times (101.28 m2/g) than original CoFe-LDH@MX, thus more favorable for capturing CR (698.25 mg/g). The results of kinetic studies demonstrate that the effective 3D composite structure enables unhindered movement of CR within the α-Fe2O3@LDH@MX. The Langmuir model can accurately describe the adsorption process of CR on the α-Fe2O3@LDH@MX, which means that the process belongs to monomolecular layer chemisorption. Molecular dynamics simulations revealed that the α-Fe2O3 interface primarily interacts with oxygen within the -SO3 group, achieving an adsorption energy up to Einteraction= −20,375.89 kcal/mol. The results of XPS analysis further revealed that interaction between Fe and O achieved the removal of CR. In this paper, the enhancement of α-Fe2O3 adsorption performance has been successfully achieved through innovative structural design. This significantly advances its potential applications and offers new insights for future material design.