Abstract: The MPX3 family of magnetic van-der-Waals materials (M denotes a first row transition metal and X either S or Se) are currently the subject of broad and intense attention for low-dimensional magnetism and transport and also for novel device and technological applications, but the vanadium compounds have until this point not been studied beyond their basic properties. We present the observation of an isostructural Mott insulator–metal transition in van-der-Waals honeycomb antiferromagnet V0.9PS3 through high-pressure x-ray diffraction and transport measurements. We observe insulating variable-range-hopping type resistivity in V0.9PS3, with a gradual increase in effective dimensionality with increasing pressure, followed by a transition to a metallic resistivity temperature dependence between 112 and 124 kbar. The metallic state additionally shows a low-temperature upturn we tentatively attribute to the Kondo effect. A gradual structural distortion is seen between 26 and 80 kbar, but no structural change at higher pressures corresponding to the insulator–metal transition. We conclude that the insulator–metal transition occurs in the absence of any distortions to the lattice—an isostructural Mott transition in a new class of two-dimensional material, and in strong contrast to the behavior of the other MPX3 compounds.