CONSPECTUS: In a conventional photovoltaic device (solar cell or photodiode) photons are absorbed in a bulk semiconductor layer, leading to excitation of an electron from a valence band to a conduction band. Directly after photoexcitation, the hole in the valence band and the electron in the conduction band have excess energy given by the difference between the photon energy and the semiconductor band gap. In a bulk semiconductor, the initially hot charges rapidly lose their excess energy as heat. This heat loss is the main reason that the theoretical efficiency of a conventional solar cell is limited to the Shockley-Queisser limit of ∼33%. The efficiency of a photovoltaic device can be increased if the excess energy is utilized to excite additional electrons across the band gap. A sufficiently hot charge can produce an electron-hole pair by Coulomb scattering on a valence electron. This process of carrier multiplication (CM) leads to formation of two or more electron-hole pairs for the absorption of one photon. In bulk semiconductors such as silicon, the energetic threshold for CM is too high to be of practical use. However, CM in nanometer sized semiconductor quantum dots (QDs) offers prospects for exploitation in photovoltaics. CM leads to formation of two or more electron-hole pairs that are initially in close proximity. For photovoltaic applications, these charges must escape from recombination. This Account outlines our recent progress in the generation of free mobile charges that result from CM in QDs. Studies of charge carrier photogeneration and mobility were carried out using (ultrafast) time-resolved laser techniques with optical or ac conductivity detection. We found that charges can be extracted from photoexcited PbS QDs by bringing them into contact with organic electron and hole accepting materials. However, charge localization on the QD produces a strong Coulomb attraction to its counter charge in the organic material. This limits the production of free charges that can contribute to the photocurrent in a device. We show that free mobile charges can be efficiently produced via CM in solids of strongly coupled PbSe QDs. Strong electronic coupling between the QDs resulted in a charge carrier mobility of the order of 1 cm(2) V(-1) s(-1). This mobility is sufficiently high so that virtually all electron-hole pairs escape from recombination. The impact of temperature on the CM efficiency in PbSe QD solids was also studied. We inferred that temperature has no observable effect on the rate of cooling of hot charges nor on the CM rate. We conclude that exploitation of CM requires that charges have sufficiently high mobility to escape from recombination. The contribution of CM to the efficiency of photovoltaic devices can be further enhanced by an increase of the CM efficiency above the energetic threshold of twice the band gap. For large-scale applications in photovoltaic devices, it is important to develop abundant and nontoxic materials that exhibit efficient CM.