Enhanced-oxidation of 4H-SiC and interface modification with BaO2 was investigated. The enhanced oxidation of 4H-SiC was drastically dependent on pre-deposited BaO2 thickness. At the oxidation time of 300 min, oxide thicknesses for BaO2 of 2.8 nm and 7.8 nm were 91.8 nm and 26.2 nm, respectively. The physical state of Ba in the oxide was investigated by XPS and 2D-GIXD. At thick BaO2 with a thickness of over 6.4 nm, bridged oxygen and non-bridged oxygen were observed in O1s state. This results shows barium silicate was formed in SiO2 at BaO2 thickness of over 6.4 nm.