Determination of organic acids and inorganic anions in serum and urine samples provide important information for pathological diagnosis of inborn disorders.In order to determine a large group of organic and inorganic anions with physiological interest simultaneously in human serum and urine samples, a new analytical procedure based on capillary zone electrophoresis (CZE) with indirect UV detection at 210 nm in a background electrolyte (3mM BTA, 1.5mM TEPA and 15mM Tris) is developed to enable a rapid determination of a desired group of organic and inorganic anions upon close matching of their mobility with a carefully selected chromophore.