The phosphorus (P) adsorption properties of an iron [Fe(0)]-rich substrate (IRS) composed of iron scraps and activated carbon were investigated based on iron–carbon micro-electrolysis (IC–ME) and compared to the substrates commonly used in constructed wetlands (CWs) to provide an initial characterization of the [Fe(0)]-rich substrate. The results showed that P was precipitated by Fe(III) dissolved from the galvanic cell reactions in the IRS and the reaction was suppressed by the pH and stopped when the pH exceeded 8.90 ± 0.09. The adsorption capacity of the IRS decreased by only 4.6% in the second round of adsorption due to Fe(0) consumption in the first round. Substrates with high Ca– and Mg–oxide contents and high Fe– and Al–oxide contents had higher P adsorption capacities at high and low pH values, respectively. Substrates containing high Fe and Al concentrations and low Ca concentrations were more resistant to decreases in the P adsorption capacity resulting from organic matter (OM) accumulation. The IRS with an iron scrap to activated carbon volume ratio of 3:2 resulted in the highest P adsorption capacity (9.34 ± 0.14 g P kg−1), with minimal pH change and strong adaptability to OM accumulation. The Fe(0)–rich substrate has the considerable potential for being used as a CW substrate.