A specific method for the separation and detection of non-UV-absorbing polyelectrolytes has been developed. The analysis of such polyelectrolytes by liquid chromatography is nearly impossible due to strong ionic interactions and charge density effects. CE makes use of these charge density effects and thus enables for proper separation. A capacitively coupled contactless conductivity detector has been applied for the detection in CE. A low molar mass poly(acrylic acid) sodium salt standard (PAA1.3k) was separated in free solution CE and detected with the contactless conductivity detector. Different amphoteric electrolytes have been tested for their applicability as BGE for the separation of polyelectrolytes with conductivity detection. It has been shown that the best detection results are obtained with an arginine-sorbate buffer.