In this study, rhenium-nickel (Re-Ni) films were formed by electroless deposition on conductive (Cu) and non-conductive (SiO2) substrates. Different bath compositions were evaluated, aiming to achieve high Re-content. Both sodium hypophosphite and dimethylamine-borane were used as reducing agents. Films containing up to 75 at% Re were obtained. The influence of nickel concentration in the solution on alloy composition, deposition rate and surface morphology were determined. It is shown that Ni2+ acts as a catalyst for the in situ reduction of the perrhenate ion, in a manner similar to what was proposed for electroplating of the same alloy. The rate of electroless plating is similar to that found in electroplating at an applied current density of 50 mA cm(-2). While pure Re cannot be deposited from our electroless plating baths, the addition of even a very small amount of Ni2+ ions (0.25 mM) is enough to start the induced codeposition of Re. Proper selection of the bath composition can lead to fine control of the alloy thickness and its Re-content, thus making it potentially attractive for thin barrier layers. (C) 2011 Elsevier Ltd. All rights reserved.