Metallic nanolayered thin films/foils, in particular Ni/Al multilayers, have been used to promote joining. The objective of this work is to evaluate the thermal stability of nanoscale metallic multilayers with potential for joining applications. Multilayers thin films with low (Ti/Al and Ni/Ti), medium (Ni/Al) and high (Pd/Al) enthalpies of exothermic reaction were prepared by dual cathode magnetron sputtering. Their thermal stability was studied by: i) differential scanning calorimetry combined with X-ray diffraction (XRD), ii) in-situ XRD using cobalt radiation, and iii) in-situ transmission electron microscopy. It was possible to detect traces of intermetallic or amorphous phases in the as-deposited short period (bilayer thickness) multilayers, except for the Ti/Al films where no reaction products that might be formed during deposition were identified. For short periods (below 20 nm) the equilibrium phases are directly achieved upon annealing, whereas for higher periods intermediate trialuminide phases are present for Ti/Al and Ni/Al multilayers. The formation of B2-NiTi from Ni/Ti multilayers occurs without the formation of intermediate phases. On the contrary, for the Pd-Al system the formation of intermediate phases was never avoided. The viability of nanoscale multilayers as "filler" materials for joining macro or microparts/devices was demonstrated. (C) 2014 Elsevier B.V. All rights reserved.