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A review of the use of the Doehlert matrix as a chemometric tool for the optimization of methods in analytical chemistry and other sciences is presented. The theoretical principles of Doehlert designs are described, including the coded values for the use of this matrix involving two, three, four and five variables. The advantages of this matrix in comparison with other response surface designs, such as central composite and Box–Behnken, designs are discussed. Finally, 57 references concerning the application of Doehlert matrices in the optimization of procedures involving spectroanalytical, electroanalytical and chromatographic techniques are considered.