For　the　system　of　Ce(NO3)(2)　center　dot　6H(2)O　and　urea　solution　during　homogeneous　precipitation　method,　X-ray　diffraction　(XRD),　infrared　spectrum　(IR)　and　especially　X-ray　photoelectron　spectroscopy　(XPS)　were　used　to　study　and　characterize　the　product　structure,　variety　of　cerium　ion　valence,　compound　surface　character　and　kernel　electronic　configurations.　The　results　of　XRD　and　IR　showed　that　calcination　temperature　had　a　great　effect　on　the　cerium　ion　valence.　The　products　are　orthorhombic　Ce2O(CO3)(2)　center　dot　H2O　with　valence　III　by　using　homogeneous　precipitation　method　directly.　When　heated　from　the　temperature　200　degrees　C　to　250　degrees　C,　the　product　of　CeO(CO3)(2)　center　dot　H2O　with　valence　VI　was　finally　changed　into　stable　CeO2　with　valence　IV.　XPS　was　used　to　study　the　surface　character　and　kernel　electronic　configurations　of　the　three　different　compounds　through　fine　scanning　of　O(1s),　Ce(3d)　and　Ce(4d)　apices,　and　the　results　approved　that　the　compounds　with　different　valences　are　caused　by　the　different　valence　electronic　configurations　of　the　products.