The coupling of capillary electrophoresis (CE) with capacitively coupled contactless conductivity detection (C4D) has become convenient analytical method for determination of small molecules that do not possess chromogenic or fluorogenic group. The implementations of CE with C4D in the determination of inorganic and organic ions and amino acids in biomedical field are demonstrated. Attention on background electrolyte composition, sample treatment procedures, and the utilize of multi‐detection systems are described. A number of tables summarizing highly developed CE‐C4D methods and the figures of merit attained are involved. Lastly, concluding remarks and perspectives are argued.