Electrostatic charges on individual spray droplets were measured using a refined form of the Millikan oil drop method. The measurement system consisted of three main sections; a droplet generation cell, a settling column and a charge measurement chamber. The trajectories required for calculation of charge were determined using a high-speed motion analyzer coupled to a long-focal-length microscope. Charges on droplets were manipulated by the addition of surface-active agents into the spray solution. Droplet charge was a function of the type and concentration of the surfactant added. For ionic surfactants, it showed a maximum at low surfactant concentrations, decreased with further surfactant addition and was constant after the CMC. The charge on cationic surfactants was always more than that observed with the anionic surfactants. Nonionic surfactants displayed a steady increase in droplet charge with increasing concentration. The charges were levier compared to the ionic surfactants. (C) 2000 Elsevier Science Ltd. All rights reserved.