Various sorbents recommended for solid phase extraction (SPE) in sample preparation procedures were studied for use in combination with capillary isotachophoresis (ITP). They were very efficient in achieving trace concentration levels (low ppb, i.e., low parts per 109) for different types of ITP analytes present in environmental and biological matrices. A macroporous carbon sorbent was convenient for sample preparation in ITP analysis of short chain fatty acids (C4–C9) in drinking water. Chelating sorbents based on hydroxyalkyl methacrylate matrix with salicylate, thioglycolate and 8-hydroxyquinolinate functionalities were found to be very suitable for preconcentration of heavy metals with an inherent sample clean-up. An octadecyl-bonded silica sorbent enabled in ITP a photometric detection of -aminobutyrate (labeled with a 2,4,6-trinitrophenyl group) at concentrations considerably lower than required for the determination of this amino acid in cerebrospinal fluid (5·10–8 mol/l).