Zero-valent aluminum (Al0) is an excellent electron donor with extremely low redox potential (E0(Al3+/Al0) = − 1.667 V) that could directly activate the green oxidant O2, producing reactive oxygen radicals to effectively degrade pollutants in the Al0/O2 system. However, the surface of Al0 is covered with a dense oxide film and easily re-passivated under neutral or alkaline conditions after modification. This is why it is currently mostly used at a pH of less than 4 and an induction period is required. In this study, a novel composite material, Al0-FeSO4-EDTABM, was prepared using Al0 with surface modification using FeSO4·7H2O crystals and the common ligand ethylenediaminetetraacetic acid (EDTA) through environmentally friendly one-pot mechanical ball milling (BM) to destroy the oxide film of Al0 and stimulate its activity. The properties and mechanism of the activation of molecular oxygen by Al0-FeSO4-EDTABM composites were discussed in detail. At an initial pH range of 2.5 to 11.0, the model pollutant phenol could be efficiently removed by over 92 % through the activation of molecular oxygen, without requiring an induction period. During the BM process, FeSO4·7H2O and EDTA effectively disrupted the oxide film on the surface of Al0 and prevented secondary passivation. During the degradation reaction, Al0-FeSO4-EDTABM facilitated the generation of active oxygen radicals mainly through a heterogeneous Fenton-like process. In conclusion, the innovative Al0-based composite/O2 system presents a simple and potential new method for preparing solid Fenton reagents with promising practical applications.