In this work, distillation curves (ASTM D86) associated with multivariate calibration (PLS-Partial Least Squares) were used to predict MON (motor octane number) and RON (research octane number) parameters of automotive fuel RMSEC getting values (Root Mean Square Error of Calibration) and RMSEP (Root Mean Square Error of Prediction) smaller than the literature. RMSEC values obtained were 0.051 and 0.078, and RMSEP values were 0.063 and 0.085 for MON and RON, respectively. These low values along with high accuracy, when compared to standard test methods (ASTM D2700 and ASTM D2999), indicated that the PLS models were efficient to predict MON and RON values and can be used as an alternative to control quality for automotive gasoline. (C) 2012 Elsevier Ltd. All rights reserved.