The on-line monitoring of the droplet/particle size distributions is very important to ensure the quality and applicability of various products in heterogeneous systems. For this reason, the main objective of the present work was to study the usage of the focused beam reflectance measurement (FBRM) technique for monitoring of liquid-liquid dispersions (styrene dispersion in aqueous solutions) and suspension polymerization of styrene. To do better understand the FBRM technique in these systems, the effects of surfactant concentrations, agitation speed and ambient light were evaluated during the in-line monitoring of average chord lengths and chord-length distributions (CLD) at different operation conditions in batch experiments. In addition, a preliminary investigation of the optimal probe position was conducted in the polymerization experiments. It is shown that the FBRM technique is sensitive to variations of particle sizes in the characteristic ranges of particle diameters of typical styrene suspension polymerizations, being useful for monitoring and also control applications that require the on-line characterization of CLD in real time in liquid-liquid dispersions and polymerization systems. POLYM. ENG. SCI., 56:309-318, 2016. (c) 2015 Society of Plastics Engineers