Nano‐liquid chromatography (nano‐LC) and CEC are microfluidic techniques mainly used for analytical purposes. They have been applied to the separation and analysis of a large number of compounds, e.g., peptides, proteins, drugs, enantiomers, antibiotics, pesticides, nutraceutical, etc. Analytes separation is carried out into capillaries containing selected stationary phase. The mobile phase is moved either by a pump (nano‐LC) or by an EOF, respectively. The two tools can offer some advantages over conventional techniques, e.g., high selectivity, separation efficiency, resolution, short analysis time and consumption of low volumes of mobile phase. Flow rates in the range 50–800 nL/min are usually applied. The low flow rate reduces the chromatographic dilution increasing the mass sensitivity. Special attention must be paid in avoiding peak dispersion selecting the appropriate detector, injector and tube connection. Finally due to the low flow rate these microfluidic techniques can be easily coupled with mass spectrometry.