A dynamic approach has been proposed for the ultrasound-assisted extraction of twenty phenolic compounds from alperujo, a semisolid waste from the olive oil industry, that is a representative example of samples with a complex matrix. Multivariate methodology was used to carry out a detailed optimisation study of both the separation-determination and extraction steps in terms of resolution-analysis time and extraction efficiency, respectively. Consequently, the proposed method was able to extract the target analytes in 13 min; then, after dilution and centrifugation, the extract was injected into the capillary electrophoresis-diode array detection system for individual separation determination in 11 min. No cleanup of the extract was required. This method is less time-consuming, more selective and provides a larger information level than the Folin-Ciocalteau spectrophotometric method. Alperujo was demonstrated to be a powerful source of phenolic compounds, particularly as compared with olive oil--8680 versus 50-1200 microg/g.