The electrostatic barrier of a Au/1.4 nm HfO2/0.8nm SiO2/Si(001) structure was mapped with ballistic hole emission microscopy on p-type silicon substrates to nanoscale dimensions over a square micrometer. The 1.4 nm HfO2 layer showed three concentrations of barrier heights localized in different regions of the sample. These concentrations are consistent with the barrier heights of HfO2/Si-p, native SiO2/Si-p, and one centered at −0.45eV. The latter barrier height is attributed to an ultrathin HfO2 (1–3 monolayers). This study demonstrates the power of electrostatic barrier mapping to visualize complex and nonuniform interfaces.