Distillers dried grains and solubles (DDGS) were investigated with attenuated total reflection FT-IR spectroscopy both directly in their solid state and as the isolated oils (fat fractions). The collected spectra were evaluated in a first step with principal component analysis (PCA) according to the botanical origin (corn, rice, wheat) and the geographical origin (Canada, China, European Union, India, United States) of the DDGS. In a second step, statistical models were constructed for the characterization of the botanical and geographical origin using linear discriminant analysis (LDA) and soft independent modeling of class analogy (SIMCA). For this purpose, the botanical origin was investigated more deeply for corn and wheat as the most important raw materials used for DDGS production. Also, the geographical origin was investigated exemplary for corn DDGS, derived from China and the United States. Models were validated by a randomized batchwise procedure and showed satisfactory classification rates, in most cases better than 80% correct classification.