A polystyrene (PS)/rubber blend compatibilized with PS-g-rubber copolymer, prepared via emulsion polymerization using redox initiator system, is used to investigate the utilization of central composite design (CCD) and artificial neural network (ANN) approaches in correlating polymerization conditions to mechanical properties (tensile strength and abrasion loss) of unfilled compound vulcanizates. The conditions were manipulated by changing four factors: reaction temperature and time, percentage of deproteinized rubber in the mixture containing natural rubber, and amount of chain transfer agent. The results show that the relationships between the conditions and the mechanical properties for compatibilized PS/rubber blend are too complex to be explained by polynomials, but are well described by the ANN models, developed for each response. In addition, simulation results for the tensile strength response as a function of those factors using the obtained ANN are in agreement with literature, whereas those results for the abrasion loss do not quite agree with literature due to the interference of the large measurement error. This suggests that only experimental data with high precision should be used to train an ANN to achieve a model with not only best performance but also high reliability.