LIBS is a developing analytical technique, which is used to perform qualitative and semi-quantitative elemental analysis of materials (solid, liquid and gas). Recently LIBS became an attractive technique to be used for geological samples, due to its advantages such as fast data collection and the lack of sample preparation. This study is done to improve analytical methods for geochemical analysis of samples during different exploration phases (Mining, filed analysis, etc.), to be used in the future as a real-time analysis method to save money and time spent in labs. In this work, LIBS has been used to differentiate between some geological samples gathered from different areas: South Africa and Namibia. Using principal component analysis (PCA), it was found that LIBS was able to differentiate between the samples even those of the same area. The results from the LIBS technique were correlated with subsequent analysis of the same samples by Particle-Induced X-ray emission (PIXE).