In this paper, the generation mechanism of oxidation products during the oxidation of the polystyrene‐block‐poly(ethylene‐co‐1‐butene)‐block‐polystyrene copolymer (SEBS)/poly(propylene) (PP) blend in air atmosphere is investigated using temperature‐dependent FTIR combined with 2D correlation infrared spectroscopy. Differential scanning calorimetry, thermogravimetric analysis, and perturbation‐correlation moving‐window 2D correlation FTIR spectroscopy find three processes associated with SEBS/PP oxidative degradation. The 2D correlation analysis is used to study the sequential order of groups' movement of reactants and oxidation products involved in the main oxidation. It is found that the main oxidation starts from the molecular chains of PP and EB blocks of SEBS. It firstly forms COC structure between the molecular chains of PP and the EB blocks, resulting in the cross‐linked structure. Aliphatic ketones are formed via the β‐scission of the main chains of PP or the EB blocks. Then, aliphatic ketones are converted into aliphatic esters. After the above reactions, the S blocks of SEBS begin to oxidize. The S blocks are generated into aromatic ketones through β‐scission. The formation of lactones in the molecular chains of PP and EB blocks is followed via the radical biting back. Finally, aromatic ketones generated from the S blocks are converted into aromatic esters through the reactions of Norrish I, the radical coupling, and so on.