The Volta potential is an electron-sensitive parameter and describes the thermodynamic propensity of a metal to take part in electrochemical reactions. It has found widespread acceptance among corrosion researchers due to its connection to the corrosion potential and its easy measurability in local scale, being often used to study localised corrosion phenomena and micro-galvanic activities. The principle object of this paper is to provide a comprehensive, fundamental insight into the meaning of the Volta potential and to define a polarity convention of measured potentials by the scanning Kelvin probe force microscopy (SKPFM) in order to assess local nobilities in microstructures. Conditions to relate the Volta potential with the mixed-potential theory are discussed and a possible connection to corrosion phenomena explained. The limitations of the Volta potential as well as the SKPFM technique are also aimed to be explained, with some practical information to maximise the output of high quality data.