Silver has been photoelectrodeposited at p-MoSe2 surfaces. These surfaces were analyzed by electron spectroscopy for chemical analysis (ESCA), auger electron spectroscopy(AES), scanning electron microscopy (SEM), and photovoltammetric methods. AES depth profiles and ESCA spectra show that MoSe2 reacts with silver by a displacement reaction that produces Ag2Se and MoO3. The dissolution of the MoO3 is evident from the AES depth profiles. Photovoltammetric studies of p-MoSe2 with different amounts of electrodeposited silver were done in 5 mM AgNO3 and 0.25 M KNO3 aqueous solutions. A continuous shift in the onset photopotential for the reduction of Ag+, with a decrease in the photovoltage, was observed concomitant with an increase in the photoelectrodeposited silver. This photoelectrochemical change is mainly due to the surface reaction of silver atoms with MoSe2, which creates the semimetallic Ag2Se phase, thus increasing the conductivity of the substrate.