With the discovery of colossal magnetoresistance materials and high-temperature superconductors, Mott insulators can potentially undergo a transition from insulating state to metallic state. Here, in molecular ferroelectrics system, a Mott insulator of (C7H14N)3V12O30 has been first synthesized, which is a 2D organic–inorganic ferroelectric with composition of layered vanadium oxide and quinuclidine ring. Interestingly, accompanied by the ferroelectric phase transition, (C7H14N)3V12O30 changes sharply in conductivity. The occurrence of a Mott transition has been proven by electric transport measurements and theoretical calculations. This research has significantly expanded the applicative horizons of ferroelectric materials, and offering an ideal platform for the investigation of strongly correlated electron systems.