Sampling agricultural soils for contaminants is relatively new. Existing standard sampling protocols used for the evaluation of soil nutrients are likely insufficient for contaminants. The main reasons are the very low analyte levels and differences in heterogeneity between nutrients and contaminants. To evaluate the adequacy of existing sampling protocols or to develop new protocols, a systematic scientific approach is needed. This approach begins with the development of the Sample Quality Criteria followed by a realistic understanding of the properties of the material to be sampled, most notably its heterogeneity. The Sample Quality Criteria and material properties are inputs into the Theory of Sampling. With these inputs, the Theory of Sampling can be used to determine the specifics of the sampling protocol (e.g., mass, number of increments, tool selection) that must be implemented to control error to reliably estimate the concentration of the analyte(s) of interest. Development of sampling protocols in this manner will ensure sample representativeness and therefore improve data equivalency among various parties involved. This is the only way to provide a sound technical basis for defensible decision making to ensure increased safety of food and feed, specifically with respect to contaminants in agricultural soils.