Studies have been made of dark and photoconductivity in thin anthracene single crystals using a Ce4+ solution as one electrode and a 1MNaCl solution as the other electrode. It was found that the Ce4+ electrode was capable of injecting holes into anthracene in the dark, the saturation current at 15 000 v/cm being about 1 μa/cm2. This current was observed when the Ce4+ electrode was at a positive potential. With the same polarity, it was found that there was practically no increase in the saturation current upon illumination of the crystal with 3650 or 4300 A light; at low voltages there was a distinct photoeffect which was attributed to the emptying of polarization producing traps, thus increasing the internal field. The saturation current was proportional to the sixtenths power of the Ce4+ concentration. At low voltages, the current was very small until a certain voltage, referred to as the onset voltage, was reached, after which the current increased rapidly. The onset voltage was larger for the dark current than for the photocurrent. The efficiency of carrier production by the Ce4+ ion was about 10—10 based on a simple collision hypothesis. Possible explanations for this low efficiency were advanced but no definite mechanism was chosen. The use of Ce3+ ion was without effect in increasing either the dark or photocurrent. Using a positive electrode of I2 in glacial acetic acid, it was found that there was practically no hole injection, in contrast with the marked hole injecting characteristics of the aqueous I2–I— electrode. Furthermore, the Ce4+ and I2–I— electrodes were ineffective with naphthalene. These results are explained by reference to a criterion for hole injection IA—WE—Ex<0, where WE is the work function of the electrode, IA is the ionization energy of anthracene in the solid, and Ex is the externally supplied energy (optical, thermal, electric field).