The photoelectric emission process is considered to be the dominant mechanism for charging of cosmic dust grains in many astrophysical environments. The grain charge and equilibrium potentials play an important role in the dynamical and physical processes that include heating of the neutral gas in the interstellar medium, coagulation processes in the dust clouds, and levitation and dynamical processes in the interplanetary medium and planetary surfaces and rings. An accurate evaluation of photoelectric emission processes requires knowledge of the photoelectric yields of individual dust grains of astrophysical composition as opposed to the values obtained from measurements on flat surfaces of bulk materials, as it is generally assumed on theoretical considerations that the yields for the small grains are much different from the bulk values. We present laboratory measurements of the photoelectric yields of individual dust grains of silica, olivine, and graphite of ~0.09-5 μm radii levitated in an electrodynamic balance and illuminated with UV radiation at 120-160 nm wavelengths. The measured yields are found to be substantially higher than the bulk values given in the literature and indicate a size dependence with larger particles having order-of-magnitude higher values than for submicron-size grains. © 2006. The American Astronomical Society. All rights reserved.