The cetane number (CN) is one of the most important parameters regarding diesel fuel oil quality, mainly ignition properties. Traditionally, the CN determination is performed by a quite laborious and high-cost method on an explosion engine. On the other hand, nuclear magnetic resonance (NMR) spectroscopy is increasing as a versatile tool for quality control in several areas, such as petroleum and fuels, which permits the fast and direct investigation on samples. In this work, two NMR-based methods for CN determination based on multivariate calibration were developed with advantages of time saving, without the need of any sample treatment.