Recently, the oxidative functionalization of double-fused-pentagon (DFP)-containing chlorofullerenes #271C50Cl10 and #913C56Cl10 was carried out, resulting in two monoepoxides with the oxygen atom added at the ortho site of pentalene on the DFP moiety. To uncover the reactivity of isolated-pentagon-rule violating fullerenes upon oxidation, two possible formation processes (ozone molecule and oxygen radical served as oxidation reagents) of these two oxides were systematically investigated through density functional theory calculations. For the ozone oxidation, two possible pathways were explored, and the results indicate that the biradical mechanism Pathos-RACDP is kinetically more favorable than Pathos-RABP, where R, A, and P represent reactants, ozonide intermediates, and oxidation products and B, C, and D represent another three oxygen-containing intermediates. The products obtained by ozone oxidation ([6,6]-55-closed epoxides P-C3-C29 for #271C50Cl10 and P-C42-C43 for #913C56Cl10 with oxygen atom added at the shortest and highest HOMO-contribution bonds) are consistent with experimental observations. However, the oxygen radical additions on these two chlorofullerenes favor generation of the [5,6]-66-open oxidoannulene adducts P-C3-C2 and P-C42-C54, respectively. Subsequent analyses of their geometrical features and structural stabilities suggest that these two oxidoannulene adducts are energetically unfavorable and could be converted to more stable epoxides mentioned above by undergoing a pirouette-type transition state. In these two diverse oxidation procedures, the favorable C-C bonds for ozone attacking and C atoms for oxygen-adsorption are rationalized in terms of their bond lengths and HOMO contributions as well as pyramidalization angles.