In this article, a method for in situ synthesis of silver benzene-dithiolate hybrid films is presented. Silver nanoparticles, generated on ZrO2 films, are transformed into silver benzene 1,4-dithiolate or, partially, into silver benzene 1,2-dithiolate after sample immersion in the corresponding thiol solutions. These transformations occur at room temperature owing to the catalytic action of ZrO2. It is also shown that TiO2 in place of ZrO2 is very efficient, both for the catalytic generation of silver nanoparticles and for their further transformation in benzene 1,4-dithiolate compound. This latter semiconductor has an optical bandgap of about 3 eV and the film is made of touching nanoparticles in an amorphous state. Our work has potential applications in the electronic and photovoltaic fields. (C) 2015 Published by Elsevier B.V.