Resistive switches, which are also known as memristors, are low-power, nanosecond response devices that are used in a range of memory-centric technologies. Driven by an externally applied potential, the switching mechanism of valence change resistive memories involves the migration, accumulation and rearrangement of oxygen vacancies within a dielectric medium, leading to a change in electrical conductivity. The ability to look inside these devices and understand how morphological changes characterise their function has been vital in their development. However, current technologies are often destructive and invasive. Here, we report a non-destructive optical spectroscopy technique that can detect the motion of a few hundred oxygen vacancies with nanometre-scale sensitivity. Resistive switches are arranged in a nanoparticle-on-mirror geometry to exploit the high optical sensitivity to morphological changes occurring in tightly confined plasmonic hotspots within the switching material. Using the approach, we find that nanoscale oxygen bubbles form at the surface of a strontium titanate memristor film leading ultimately to device breakdown on cycling.