Emulsion and suspension polymerizations are important industrial processes for polymer production. The end-user properties of polymers depend strongly on how the polymerization reactions proceed in time (i.e. a batch or semicontinuous, rate of reagents feeding, etc.). In other words, these reactions are process dependent, which makes the successful process control a key point to ensure high-quality products. In several process control strategies the on-line monitoring of reaction performance is required. Due to the multiphase nature of the emulsion and suspension processes, there is a lack of sensors to perform successful on-line monitoring. Near infrared and Raman spectroscopies have been pointed out as useful approaches for monitoring emulsion and suspension polymerizations and several applications have been described. In such instance, the chemometric approach on relating near infrared and Raman spectra to polymer properties is widely used and has proven to be useful. Nevertheless, the multiphase nature of emulsion and suspension polymerizations also represents a challenge for the chemometric approach based on multivariate calibration models and demands the development of new methods. In this work, a set novel results is presented from the monitoring of 15 batch emulsion reactions that show the chemometric challenge to be faced on development of new methods for successful monitoring of processes taken under dispersed medium. In order to discuss these results, several chemometric approaches were revised. It is shown that Raman and NIR spectroscopic techniques are suitable for on-line monitoring of monomer concentration and polymer content during the polymerizations, as well as medium heterogeneity properties, i.e. average particle size. It is also shown that Hotteling and Q statistics, widely used in chemometrics, might fail in monitoring these reactions, while an approach based on principal curves is able to overcome such restriction.