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Abstract Nitrogen vacancy (NV) centers, optically active atomic defects in diamond, have attracted tremendous interest for quantum sensing, network, and computing applications due to their excellent quantum coherence and remarkable versatility in a real, ambient environment. Taking advantage of these strengths, this paper reports on NV‐based local sensing of the electrically driven insulator‐to‐metal transition (IMT) in a proximal Mott insulator. The resistive switching properties of both pristine and ion‐irradiated VO₂thin film devices are studied by performing optically detected NV electron spin resonance measurements. These measurements probe thelocaltemperature and magnetic field in electrically biased VO₂devices, which are in agreement with theglobaltransport measurement results. In pristine devices, the electrically driven IMT proceeds through Joule heating up to the transition temperature while in ion‐irradiated devices, the transition occurs nonthermally, well below the transition temperature. The results provide direct evidence for nonthermal electrically induced IMT in a Mott insulator, highlighting the significant opportunities offered by NV quantum sensors in exploring nanoscale thermal and electrical behaviors in Mott materials.