The Fe(II)/CaO₂ system with a stable oxidant and a low-cost homogeneous activating agent has been considered as a prospective process for the disposal of wastewater. The system was constructed to treat sewage sludge hydrothermal carbonization aqueous phase (HTC-AP) in this study. As the hydrothermal temperature increased, the organics in the HTC-AP were first decomposed and then cyclized, while the Maillard reaction occurs throughout the stage. The oxidation efficiency of the Fe(II)/CaO₂ system was related to the composition of organics in HTC-AP, and the removal of dissolved organic carbon (DOC) by the system was 38.56 % in the HTC-AP obtained by hydrothermal treatment at 220 °C. Redundancy analysis showed that the low molecular weight organics, hydrophobic acids, and hydrophobic neutral components were beneficial to DOC removal, while Maillard products and cyclization products were hard to be oxidized to CO₂ and H₂O. The CN functional group of the protein facilitated DOC removal, and some organics in HTC-AP were oxidized to acids and phenols. The energy input to remove DOC in Fe(II)/CaO₂ system was 27.74 MJ per kg carbon. This study provides a low-energy consumption Fe(II)/CaO₂ system for the post-treatment of HTC-APs and explores the applicability of the system.