Structural, compositional, optical, and electrical properties of CuInSe 2 thin films grown by rf reactive sputtering from a Se excess target in Ar/H 2 atmospheres are presented. The addition of H 2 to the sputtering atmospheres allows the control of stoichiometry of films giving rise to remarkable changes in the film properties. Variation of substrate temperature causes changes in film composition because of the variation of hydrogen reactivity at the substrate. Measurements of resistivity at variable temperatures indicate a hopping conduction mechanism through gap states for films grown at low temperature (100–250 °C), the existence of three acceptor levels at about 0.046, 0.098, and 0.144 eV above valence band for films grown at intermediate temperature (250–350 °C), and a pseudometallic behavior for film grown at high temperatures (350–450 °C). Chalcopyrite polycrystalline thin films of CuInSe 2 with an average grain size of 1 μm, an optical gap of 1.01 eV, and resistivities from 10^-1 to 10³ Ω cm can be obtained by adding 1.5% of H 2 to the sputtering atmosphere and by varying the substrate temperature from 300 to 400 °C.