A direct, completely automated calibration procedure in capillary electrophoresis (CE) is presented. The manual calibration operations involved in analytical methods, such as external calibration, standard addition, and internal standard, were accomplished with a continuous flow system (CFS) coupled to commercial capillary electrophoresis equipment via a programmable arm. The system was managed by the proper CE microprocessor and allowed automatic calibration and direct quantification of the analytes in the sample without any manual pretreatment, therefore avoiding or minimizing manually associated errors. The whole system including peristaltic pumps and the programmable arm was connected via an electronic interface and completely controlled by a computer using a program written in GW-BASIC. The potential of this new CFS-CE arrangement was assessed by applying it to samples containing selected compounds.