Using a modified surface forces apparatus, we have simultaneously measured the friction and triboelectrification between both similar and dissimilar molecularly smooth hexadecanethiol-coated metal surfaces on mica substrates. On shearing dissimilar surfaces, the tribocurrent increases dramatically as the load or pressure is increased, with large fluctuations about the mean. Neither charge transfer nor fluctuations are observed when the symmetric surfaces are sheared against each other. We also find that the type of friction, i.e., stick-slip or smooth sliding, the load and friction force, the sliding distance, and recent previous history have additional fine influences on the triboelectrification. Our results suggest that frictional dissipation induces electronhole formation and charge transfer between two shearing surfaces due to molecular-level roughness and defects and local dielectric constant changes, giving rise to the observed tribocurrents.