Abstract Much capillary electrochromatography (CEC) work is carried out on bonded silica packings which offer many advantages: the number of such packings which are available; the fact that the chemistry of bonding and the separation process are fairly well understood; and the possibility of the transfer to CEC of existing HPLC methods. Packing methods for the preparation of CEC columns have been investigated. The problems inherent in the use of burned-in frits remains an obstacle, but can be at least partially overcome by minimising the length and by silanisation. The influence of a variety of mobile phase variables on aspects of CEC is in agreement with theory for: ionic strength, organic content (including isoeluotropy), and pH. Temperature can be used as a variable to change column selectivity in CEC. The influence of pH on electroosmotic flow (EOF) by changing the degree of ionisation of residual silanol groups is similar for a wide range of neutral bonded groups, but is much less marked for bonded sulphonic acid groups. The EOF may be reversed for bonded groups containing nitrogen.