The thermal stability of crystalline-amorphous interfaces was investigated in Fe/FeW nanomultilayers (NMs), where the alloy layers were amorphous in the as-sputtered state with concentrations of Fe-38 at.% W or Fe-67 at.% W. Compositionally driven devitrification, layer breakdown, and recrystallization were compared using both single-layer and multilayer configurations at temperatures ranging from 250 °C to 750 °C. Annealing of the NMs to 500 °C revealed destabilization in the Fe-67 W layers with the formation of crystalline-crystalline interfaces (CCIs) whereas the Fe-38 W layers remained intact with stable crystalline-amorphous interfaces (CAIs). Further annealing to 750 °C resulted in multilayer evolution and recrystallization, where breakdown of the CAIs was attributed to layer intermixing while the CCIs experienced intermetallic grooving and pinch-off. The influence of amorphous stability, composition, and intermetallic formation are discussed with respect to the NM breakdown mechanisms. This work highlights a promising strategy for exploring compositionally driven stability at the nanoscale in crystalline-amorphous alloys.