Chemical screening using reversed phase HPLC'photodiode array detection (RPLC'DAD) and RPLC'electrospray ionisation mass spectrometry (RPLC'ESI-MS) is widely applied as an approach to streamline natural products research. The full potential of this approach is demonstrated in this paper by application to the chemical screening of olive products including olive mill waste (OMW). Out of 100 biophenols previously reported in olive products, the on-line RPLC'DAD'ESI-MS was able to confirm the presence of 52 compounds in OMW. This included a number of simple phenols, flavonoids and secoiridoids. By careful examination of the combined DAD and ESI-MS data, extra information was elucidated including: the site of glycosidation on the phenol ring of hydroxytyrosol; the identity of the other luteolin-glucoside isomer as luteolin-4?-O-glucoside; identifying rutin rather than the previously reported hesperidin (and the reasons for possible mis-assignment); and the detection of diastereomers of 4-hydroxyphenylethyl alcohol-deacetoxy elenolic acid dialdehyde (4-HPEA-DEDA) and 3,4-dihydroxyphenylethyl alcohol-deacetoxy elenolic acid dialdehyde (3,4-DHPEA-DEDA).