The presence of a surface‐charge layer has been found in BaTiO3whiskers. A particular example is discussed where the surface‐charge layer completely dominated the properties of the whisker. A transition layer between the surface layer and the interior of the whisker was observed optically and found to be approximately 1 &mgr; thick. The domain structure of the whisker could be changed by applying an external axial electric field. The whisker always returned to its own unique equilibrium configuration when the field was removed. This equilibrium configuration was a direct result of the presence of the surface layer. The spontaneous polarization vector within the surface layer was saturated normal to the surfaces and toward the interior of the whisker. It was demonstrated both experimentally and analytically that this surface layer could cause spontaneous nucleation of spike‐shaped domains. These spikes extended through the surface layer and into the interior of the whisker. Nucleation occurred even in the presence of an opposing electric field. The magnitude of the potential drop across the surface layer apparently depends upon imperfections.