Despite significant progress in treatments for smoking cessation, smoking continues to be a significant public health concern, especially in young adulthood. Thus, developing a predictive model that can classify and characterize the brain-based biomarkers predicting smoking status would be imperative to improving treatment development. In this study, we applied a support vector machine-based classification method to discriminate 70 young male smokers and 70 matched nonsmokers using their diffusion tensor imaging (DTI) data. The classification procedure achieved an average accuracy of 88.6% and an average area under the curve of 0.95. The most discriminative features that contributed to the classification were primarily located in the sagittal stratum (SS), external capsule (EC), superior longitudinal fasciculus (SLF), anterior corona radiata (ACR) and inferior front-occipital fasciculus (IFOF). The following regression analysis showed a significant negatively correlation between the average RD values of the left ACR (r = -0.247, p = 0.039) and FTND. The average MD values in the right EC (r = -0.254, p = 0.034) and RD values in the right IFOF (r = -0.240, p = 0.046) were inversely associated with pack-years. Our findings indicate that the discriminative white matter (WM) features as brain biomarkers provide great predictive power for smoking status and suggest that machine learning techniques can reveal underlying smoking-related neurobiology.