To solve the adulteration problem of brown rice flour in the commodity market, a novel, accurate, and stable detection method based on time-resolved laser-induced breakdown spectroscopy (TR-LIBS) is proposed. Qualitative and quantitative analysis was used to detect five adulterants and seven different adulterant ratios in brown rice flour. Being able to excavate more information from plasma by obtaining time-resolved spectra, TR-LIBS has a stronger performance, which has been further verified by experiments. For the qualitative analysis of adulterants, the traditional machine learning models based on TR-LIBS, linear discriminant analysis (LDA), naïve Bayes (NB) and support vector machine (SVM) have significantly better classification accuracy than those based on traditional LIBS, increasing by 3–11%. The deep learning classification model based on TR-LIBS also achieved the same results, with an accuracy increase of more than 8%. For the quantitative analysis of the adulteration ratio, compared with traditional LIBS, the quantitative model based on TR-LIBS reduces the limit of detection (LOD) of five adulterants from about 8–51% to 4–19%, which effectively improves the quantitative detection performance. Moreover, t-SNE visualization proved that there were more obvious boundaries between different types of samples based on TR-LIBS. These results demonstrate the great prospect of TR-LIBS in the identification of brown rice flour adulteration.