Due to the complexity of, and low accuracy in, iron ore classification, a method of Laser-Induced Breakdown Spectroscopy (LIBS) combined with machine learning is proposed. In the research, we collected LIBS spectra of 10 iron ore samples. At the beginning, principal component analysis algorithm was employed to reduce the dimensionality of spectral data, then we applied k-nearest neighbor model, neural network model, and support vector machine model to the classification. The results showed that the accuracy of three models were 82.96%, 93.33%, and 94.07% respectively. The results also demonstrated that LIBS with machine learning model exhibits an excellent classification performance. Therefore, LIBS technique combined with machine learning can achieve a rapid, precise classification of iron ores, and can provide a completely new method for iron ores’ selection in the metallurgical industry.