Supramolecular analytical chemistry has emerged as a new discipline at the interface of supramolecular and analytical chemistry. It focuses on analytical applications of molecular recognition and self-assembly. One of the important outcomes of the supramolecular analytical chemistry is the understanding of molecular aspects of sensor design, synthesis and binding studies of sensors while using rigorous methods of analytical chemistry as a touchstone to verify the viability of the supramolecular aspects of the sensor design. This critical review provides a simplified version of the chemometric procedures involved in realizing a successful analytical experiment that utilizes cross-reactive optical sensor arrays, and summarizes the current research in this field. This review also shows several examples of use of described chemometric methods for evaluation of chemosensors and sensor arrays. Thus, this review is aimed mostly at the readers who want to test their newly-developed chemosensors in cross-reactive arrays (169 references).