Using combinatorial reactive sputtering, we have synthesised Nb–Ru–O thin films on Kapton (polyimide) with the Ru/Nb ratio from 0.5 to 1.1 in a dioxide type of environment. Based on correlative analysis, including synchrotron diffraction experiments and density functional theory, the topology of these amorphous samples is characterised by short metal–oxygen bonds and very pronounced metal–metal interactions within the second coordination shell. We suggest that the role of Nb is within bond length reduction and promotion of quantum confinement, giving rise to an increase in the Seebeck coefficient. Furthermore, these Nb–Ru–O thin films are mechanically flexible as there are no crack formation and delamination upon bending or rolling. This may be rationalised as follows. Nb–Ru–O appears ductile due to low topological connectivity and forms strong bonds with Kapton.