Thin films of high-k dielectric/ferroelectric materials such as BaxSr1−xTiO3 (BST), PbZrxTi1−xO3 (PZT) and SrBi2Ta2O9 (SBT) are currently investigated for integration into high-density CMOS technology. Characterization of these materials by SPM techniques combines imaging of the morphology and microstructure of these films and recording of various electrical parameters at the same local area. Using commercial equipment we have investigated electrical properties such as polarization and leakage current behavior of MOD/MOCVD SBT by applying electrostatic force microscopy (EFM) and conducting atomic force microscopy (CAFM). After applying bias voltages of a few volts across the SBT films between the scanning tip and the lower electrode completely polarized/reverse polarized SBT layers could be observed by EFM. Even single crystallite polarization was imaged. However, unexpectedly some films showed incomplete polarization, which may be caused by local electrical field effects. Images taken by C-AFM displayed enhancement of leakage currents in grain boundary regions, in particular at depressions between adjacent crystallites. The results achieved demonstrate that SPM techniques operated in a variety of imaging and measuring modes, provide a tremendous potential in the elucidation of the microscopic properties of high-k materials.