The invention discloses a group VB doping CaCu3Ti4O12 based pressure sensitive material and a preparation method. The general chemical composition formula of the group VB doping CaCu3Ti4O12 based pressure sensitive materia is CaCu3Ti4-xBxO12, wherein B represents one or combination of group VB elements in the periodic table of chemical elements, and x=0.001-1. The preparation method comprises thefollowing steps of compounding calcium carbonate, copper oxide, vanadium pentoxide, niobium pentaoxide and tantalum pentoxide in accordance with the stoichiometric ratio of CaCu3Ti4-xBxO12 (x=0.001-1, and B represents one or combination of group VB elements in the periodic table of chemical elements), ball milling, calcining, secondary ball milling, pelleting, forming, binder removing, high temperature sintering and the like so that Ca, Cu, Ti-O based ceramics with high permittivity and high pressure sensitive feature can be finally prepared. The invention compensates valence changes of copper ions and titanium ions in the sintering process, which can cause low voltage gradient and large leakage current, by partially replacing a +4 Ti element with a +5 element, thereby reducing the intrinsic conductivity of materials and improving the voltage gradient of the materials.