Vanadium dioxide (VO2) has received tremendous research interest in recent years for its versatile electronic application possibilities based on its reversible metal–insulator transition (MIT) behavior, which can be triggered by a large set of stimuli, such as current, electric field, or light. VO2 undergoes a phase transition from a semi-insulating monoclinic to metallic rutile phase at a low critical temperature of 68 °C, which is very close to room temperature, and compatible with any inexpensive flexible substrate. However, due to the existence of various vanadium oxide polymorphs, the synthesis of the pure monoclinic VO2 (M) phase is a challenge. In fact, the difficulty level increases further when it is to be solution-processed. However, synthesis protocol for phase-pure VO2 (M) following wet chemical routes is essential to obtain high throughput, cost-efficient, and substrate-independent fabrication routine for the large volume of devices. In this regard, in this study, we report a solution-based synthesis of ultrasmall VO2 (M) nanoparticles that are phase-pure and the small nanoparticles may easily be used to formulate inkjet printable VO2 nanoparticulate. The printed VO2 (M) films have been found to be homogeneous, crack-free and the memristor device thus fabricated has demonstrated temperature-dependent phase transition and a resistance change of more than three orders of magnitude around 68 °C; on the other hand, retention of the metallic and insulating state has also been demonstrated for 180 min.