This work describes the synthesis and the structural characterization of the La3.5-xBa4.5+x-yCayCu8O18 (0.2<x<0.4 and 0.3<y<0.5) systems, obtained by the conventional solid-state reaction method. The samples were characterized by X-ray diffraction comparing the main signals of the experimental and theoretical diffractograms with the PCW software, revealed the obtaining of an orthorhombic structure with space group Pmm2 (25) and unit cell volume V=465.5370Å3. The analysis by Raman spectroscopy allows to determine the main modes of vibration of the different bonds that are formed between the atoms in the synthesized perovskite structure.