Multiple-separation and -detection are two approaches applied at the identification of analytes in chromatography. Using them depends on the physico-chemical properties and elemental content of the analytes. When physico-chemical properties are similar multiple-separation gives better opportunities for the identification. In this case, the efficiency of the columns is very important. When analytes contain some characteristic groups as--NO2, halogen, or nitrogen atoms then multiple-detection will be more useful. The sensitivity and/or selectivity of the detectors increase reliability of identification significantly.