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The characteristic metal–insulator phase transition (MIT) in vanadium dioxide results in nonlinear electrical transport behavior, allowing VO2 devices to imitate the complex functions of neurological behavior. Chemical doping is an established method for varying the properties of the MIT, and interstitial dopant boron has been shown to generate a unique dynamic relaxation effect in individual B‐VO2 particles. This paper describes the first demonstration of an electrically stimulated B‐VO2 proto‐device which manifests a time‐dependent critical transformation temperature and switching voltage derived from the coupling of dopant diffusion dynamics and the metal–insulator transition of VO2. During quasi‐steady current‐driven transitions, the electrical responses of B‐VO2 proto‐devices show a step‐by‐step progression through the phase transformation, evidencing domain transformations within individual particles. The dynamic relaxation effect is shown to increase the critical switching voltage by up to 41% (ΔVcrit = 0.13 V) and also to increase the resistivity of the M1 phase of B‐VO2 by 14%, imbuing a memristive response derived from intrinsic material properties. These observations demonstrate the dynamic relaxation effect in B‐VO2 proto‐devices whose electrical transport responses can be adjusted by electronic phase transitions triggered by temperature but also by time as a result of intrinsic dynamics of interstitial dopants. [ABSTRACT FROM AUTHOR]