Clean water is one of the sustainable development goals. Organic dye is one of the water pollutants affecting water quality. Hence, the conversion of dyes to safer species is crucial for water treatment. The Fenton reaction using Fe as a catalyst is a promising process. However, homogeneous catalysts are normally sensitive, difficult to separate, and burdensome to reuse. Therefore, a catechol-based hypercrosslinked polymer (catechol-HCP) was developed as an inexpensive solid support for Fe (catechol-HCP-Fe) and applied as a heterogenous Fenton catalyst. The good interaction of the catechol moiety with Fe, as well as the porous structure, simple preparation, low cost, and high stability of catechol-HCP, make it beneficial for Fe-loading in the polymer and Fenton reaction utilisation. The catechol-HCP-Fe demonstrated good catalytic activity for methylene blue (MB) degradation in a neutral pH. Complete decolouration of 100 ppm MB could be observed within 25 min. The rate of reaction was influenced by H2O2 concentration, polymer dose, MB concentration, pH, and temperature. The catechol-HCP-Fe could be reused for at least four cycles. The dominant reactive species of the reaction was considered to be singlet oxygen (1O2), and the plausible mechanism of the reaction was proposed.