The use of near-infrared reflectance spectroscopy (NIRS) calibrations to predict the ingredient composition in compound feeds (i.e., inclusion percentage of each ingredient) is a complex task, regarding both the nature of the parameters to be predicted, since they are not well-defined chemical entities, and the heterogeneousness of the matrices/formulas in which each ingredient participates. The present paper evaluates the use of nonlinear regression methods, such as artificial neural networks (ANN), for developing NIRS calibrations to predict these parameters. Two of the most representative ingredients in the Spanish compound feed formulations (wheat and sunflower meal) were selected for evaluating ANN possibilities, using a large spectral library comprising a total of 7523 commercial compound feed samples; 7423 were used as training set and 100 as validation set. Three general models of networks were studied: multilayer perceptron with back-propagation training (BP), multilayer perceptron with Levenberg-Maquartd training (LM), and radial basis function nets (RBF); moreover, in accordance with a factorial design, more complex architectures were evaluated gradually, changing the number of hidden layers and hidden neurons, for the determination of the optimal network topology. For both ingredients, the best results were obtained using ANN with BP training, showing prediction error values (SEP) of 2.72% and 0.66% for wheat and sunflower meal, respectively. These SEP values showed a significant improvement (19%-49% for sunflower meal and wheat, respectively) in comparison with those obtained using calibrations developed with linear methods.