Brand classification of iron ores using laser-induced breakdown spectroscopy (LIBS) combined with artificial neural networks can quickly realize the compliance verification and guarantee the interests of both trading partners. However, its practical application is impeded by complex pretreatments and unexplained feature learning problems. According to the LIBS data characteristics of iron ores, a convolutional neural network (CNN) is designed to predict 16 types of brand iron ores from Australia, Brazil, and South Africa. The accuracies of the calibration set and the prediction set with five-fold cross-validation (5-CV) were 99.86% and 99.88%, and the value of loss function was 0.0356. Meanwhile, the established CNN method was also compared with common machine learning methods using raw spectra as input variables, and it outperformed other methods. For the first time, this work interprets the CNN's effectiveness layer by layer in self-adaptively extracting LIBS features through t-distributed stochastic neighbor embedding (t-SNE) and the quantitative data of major chemical components in iron ores. Our approach shows that deep learning assisted LIBS is able to significantly reduce manual factors in preprocessing and feature selection and has broad application prospects in the brand classification of iron ores.