Polyelectrolyte flocculation is a commonly used method for sewage sludge conditioning. The rate and extent of water removal from the flocculated sludge depends on the properties of the polyelectrolytes. This study investigates the flocculation performance of four different cationic polyelectrolytes using an in-situ laser probe which uses focused beam reflectance measurements (FBRM). It is used to characterise the floc number and size distribution of the flocculated sludge at various polyelectrolyte doses. Results show that the FBRM technique is very successful in tracking the change in particle population and chord lengths during the sludge flocculation process. The FBRM offers an alternative method for optimising the flocculation system in both selecting the flocculant and determining its optimum dose. Both the reduction in particle count for particles of less than 10 mm and the flocculation efficiency defined from the amount of the original sludge distribution remaining after flocculation correlate well with dewatering performance.