Fenton and Fenton-like reactions are regarded as high efficient methods in advanced treatment of nitrobenzene wastewater but both restrained in degradation of nitrobenzene in groundwater because of the low pH condition( less than 4 ) requirement and other problems such as secondary pollution by the irons in contaminated sites. This paper reports a new Fenton-like technology combined irons extraction from aquifer materials which were found in a nitrobenzene contaminated site in China with hydrogen peroxide catalytic oxidation. The simulate experiments were conducted to investigate the oxidation of nitrobenzene in groundwater by this method under the condition of neutral pH and 8~10°C. The comparison of different extraction agent and production rule of hydroxyl radical were both studied in this research. The results indicated that extraction had hysteresis property because the highest extracting efficiency occurred after 36h. Extraction agent DCB has the highest efficiency, for Fe3+ was 62.92% and Fe2+ was 30.17%. The highest removal efficiency could reach 80.2% while the mole ratio of nitrobenzene to H2O2 was 1:200. Three stages could found in hydroxyl radical generation process, in the first stage hydroxyl radical generated rapidly in 0~30min, then decreased slowly between 30min and 120min, at last the generation tended to be steady after 120h. The results could possess a good potential for application in the treatment of nitrobenzene contaminated groundwater and provide theoretical basis on in-situ chemical remediation technology of nitrobenzene contaminated sites.