This paper presents a new approach for identifying analytes by CE. The compound to be identified is analyzed together with the corresponding reference standard during a double injection capillary electrophoretic run. The inter-plug distance is regulated by applying an electrical field over the capillary for a predetermined time period (t(PE)). The migration time of an analyte being exposed to the partial electrophoresis was calculated from the partial migration time (tmig(p)) as described in this paper. The identification is based on the closeness of agreement between the calculated migration time (t(mig(c))) and observed migration time (t(mig)) of the reference standard. The validity of the derived equations was checked by analyzing several substances such as caffeine, melamine, acetyl salicylic acid, paracetamol, ibuprofen, metoprolol, naproxen, somatropin, several insulin analogs, as well as different pharmaceutical and natural products. The migration time ratios for the identified solutes varied between 0.996 and 1.006 (i.e., 1.001 +/- 0.005), indicating good agreement between the observed and calculated migration times.