To identify cancer from non-cancer is one of the most challenging issues nowadays in the early diagnosis of cancer. The primary issue of early detection is to choose a suitable type of sample collection to diagnose cancer. A comparison of whole blood and serum samples of breast cancer was studied using laser-induced breakdown spectroscopy (LIBS) with machine learning methods. For LIBS spectra measurement, blood samples were dropped on a substrate of boric acid. For the discrimination of breast cancer and non-cancer samples, eight machine learning models were applied to LIBS spectral data, including decision tree, discrimination analysis, logistic regression, naïve byes, support vector machine, k-nearest neighbor, ensemble and neural networks classifiers. Discrimination between whole blood samples showed that narrow neural networks and trilayer neural networks both provided 91.7% highest prediction accuracy and serum samples showed that all the decision tree models provided 89.7% highest prediction accuracy. However, using whole blood as sample achieved the strong emission lines of spectra, better discrimination results of PCA and maximum prediction accuracy of machine learning models as compared to using serum samples. These merits concluded that whole blood samples could be a good option for the rapid detection of breast cancer. This preliminary research may provide the complementary method for early detection of breast cancer.