Recently, ferroelectric tunnel junctions have attracted much attention due to their potential applications in non-destructive readout non-volatile memories. Using a semiconductor electrode has been proven effective to enhance the tunnelling electroresistance in ferroelectric tunnel junctions. Here we report a systematic investigation on electroresistance of Pt/BaTiO3/Nb:SrTiO3 metal/ferroelectric/semiconductor tunnel junctions by engineering the Schottky barrier on Nb:SrTiO3 surface via varying BaTiO3 thickness and Nb doping concentration. The optimum ON/OFF ratio as great as 6.0 × 106, comparable to that of commercial Flash memories, is achieved in a device with 0.1 wt% Nb concentration and a 4-unit-cell-thick BaTiO3 barrier. With this thinnest BaTiO3 barrier, which shows a negligible resistance to the tunnelling current but is still ferroelectric, the device is reduced to a polarization-modulated metal/semiconductor Schottky junction that exhibits a more efficient control on the tunnelling resistance to produce the giant electroresistance observed. These results may facilitate the design of high performance non-volatile resistive memories.