The sequence of Cu substituted Ca0.9La0.05Bi0.05Mn1-XCuxO3 ( x = 0, 0.025, 0.05, 0.075, and 0.1) manganite has been studied and it has effect in the structure. The samples were synthesized using the citric acid sol-gel method. The samples were sintered at 8000 C for 5 hours. The crystallography and morphological of all samples was investigated using X-Ray Diffractometer (XRD) and Scanning Electron Microscope (SEM). The Rietveld analysis of the powder x-ray diffraction shows that all the samples crystallize in orthorhombic structure with pnma space group symmetry without any impurity phase. The Cu substitution does not change the crystal structure, but it changes the grain size. SEM results showed a valid different morphological structure. The increasing Cu concentration, it made the grain size larger, despite all the samples had the same treatment.