Energy Dispersive X-ray Analysis, EDX mapping, Scanning Electron Microscope, SEM, together with X-ray Fluorescence Analysis, XRF, was carried out to extract the needed data from some metamorphic rock samples in part of the Nigerian Southwestern Precambrian Basement Complex, NSPBC. The foremost aim is to obtain the detail subsurface geological structures of the rocks within the area and to enhanced understanding of the processes and the types of metamorphic evolution in the area. The techniques involved qualitative and quantitative data analysis of the major, minor and radioactive elements present in the samples of rocks analyzed. The data helped to experimentally evaluate the rocks microstructures, and to also explore the development of magmatic and metamorphic mechanisms for the recognition of textual associations in the area. Applications of the EDX, SEM, and XRF data analysis are effortlessly done to determine the varied mixtures of Si, Al, Ca, Fe, K, Mg, and Na, in the presence of O existing in the rocks samples.The data helped in the classification and perceptive of these rocks and it was considered as a necessary tool in the knowledge of the metamorphism and origin of the Basement Complex rocks through measurement of the intensity of the emitted X-ray and its characteristics.