Photochemical/photocatalytic reaction, one of the aging pathway of biochar in soil, not only changed the physicochemical properties of biochar, but also affected the migration and transformation of pollutants. Wheat straw biochar was photocatalytic aged in a Fenton-like system using organic acid as buffer solution under light sources, the organic carbon release and surface chemical changes of biochar were investigated to illustrate the adsorption behaviors. With Fe(III) or α-Fe2O3 added, the total organic carbon (TOC) of aged biochar solution was influenced more by buffer system than light sources, with the highest of 420.59 mg L-1 in citric acid system. The production of the hydroxyl radical (OH·) at citric/Fe(III) system was higher than the oxalic/Fe(III) system under the Hg lamp and showed an increasing trend with time. With light exposure, the porous structure of the biochar altered and surface area increased from 7.613 to 29.74 m2 g-1. Meanwhile, the adsorption of cadmium ion by biochar aged in citric/Fe(III) system also showed an increased adsorption capacity with a maximum of 73.54 mg g-1. So, a well understanding of biochar physicochemical properties changes under natural ecosystem was undoubtedly useful for scientific assessment the long-term feasibility of biochar as soil remediation.