A wide variety of olive oil samples from different origins and olive types has been chemically analyzed as well as evaluated by trained sensory panelists. Six chemical parameters have been obtained for each sample (free fatty acids, peroxide value, two UV absorption parameters (K 232 and K 268), 1,2-diacylglycerol content, and pyropheophytins) and linked to their quality using an artificial neural network-based model. Herein, the nonlinear algorithms were used to distinguish olive oil quality. Two different methods were defined to assess the statistical performance of the model (a K-fold cross-validation (K = 6) and three different blind tests), and both of them showed around a 95–96% correct classification rate. These results support that a relationship between the chemical and the sensory analyses exists and that the mathematical tool can potentially be implemented into a device that could be employed for various useful applications.