In the current work, phenolic acids were analysed and their radical scavenging activity evaluated by CE, including the quantification of overlapping peaks by applying the multivariate curve resolution (MCR) method. To investigate radical scavenging activity, the solution of phenolic acids was treated with a stable free 2,2-diphenyl-1-picrylhydrazyl radical of different concentrations and the radical scavenging activity of the reaction mixture was monitored. The radical scavenging reaction was also applied to wheat bran extracts. The overlapping peaks on the electropherograms of both mixtures of standard compounds and extracts of different wheat bran varieties were resolved by using the MCR method, assuming that the overlapping compounds have different UV spectra. MCR enabled the insufficient resolution between syringic and ferulic acids to be effectively resolved.