The potentialities of capillary ITP combined with diode-array detection (DAD) with subsequent chemometric data processing have been investigated in this work. A series of different migration configurations were created using model analytes, interferents and appropriate spacers. Special attention has been paid not only to constituents migrating in fully developed ITP zones but also to the spike mode of ITP migration. The purity assessment and identity confirmation of model analytes migrating in both modes were performed by means of multivariate curve resolution and target transformation factor analysis (TTFA). Their successful applications have revealed a smart way to increase in the analytical information obtained by ITP separation even in the instance of trace analysis.