Within this work it is our intention to provide an overview of the use of arrays or microelectrodes in the characterisation of environmental samples. Electrochemical methods are often a relatively simple and inexpensive alternative to spectroscopic or chromatographic methods for the analysis of a wide range of analytes. Arrays of microelectrodes display a number of advantages over simple planar macroelectrodes and the reasons for this will be detailed within this work. We will also describe some of the most common methods for constructing microarrays. The application of these arrays for analysis of environmental samples such as soil and water for heavy metal contamination has been the major focus of research in this field and comprises much of this review. However other systems will also be detailed such as determination of various anions or other samples such as pesticides.