The Neural Network (NN) technique was applied to the calibration of an ion selective electrode (ISE) array comprising a bromide selective electrode, two chloride ISEs and one thiocyanate ISE. The measured samples were synthetic mixture solutions of chlorides and bromides in concentration ranges such that interference occurs. The NN method allowed to perform the calibration without estimating the coefficients of the Nikolskii-Eisenman theoretical relation. Only the determination of bromide was detailed. The results obtained using this method were better than those obtained using linear multivariate calibration methods.