<jats:title>Abstract</jats:title><jats:p>An HPLC‐UV‐MS method for simultaneous identification of predominant phenolics and minor nucleoside derivatives in<jats:italic> Gastrodia elata</jats:italic> was developed, which was based on their UV and MS characteristics summarized through a series of homemade reference standard experiments. Phenolics showed characteristic UV λ<jats:sub>max</jats:sub> at 267 nm, [M + NH<jats:sub>4</jats:sub>]<jats:sup>+</jats:sup> base peak in positive mode and [M–H]<jats:sup>–</jats:sup> base peak in negative mode while nucleosides exhibited UV λ<jats:sub>max</jats:sub> at 255 nm, [M + H]<jats:sup>+</jats:sup>, [M–H + 2H<jats:sub>2</jats:sub>O]<jats:sup>–</jats:sup> or [M–H + CH<jats:sub>3</jats:sub>COOH]<jats:sup>–</jats:sup>. Phenolics conjugates mainly underwent the consecutive loss of gastrodin residue (–268 U) and the combined loss of H<jats:sub>2</jats:sub>O and CO<jats:sub>2 </jats:sub>from the citric acid unit under negative MS/MS conditions whereas nucleosides simply lost the ribose (–132 U) under positive MS/MS conditions. According to these characteristics, a special pattern under MS/MS conditions and reported compound data for<jats:italic> G. elata</jats:italic> in the literature, not only 15 phenolics were identified but also 6 nucleoside derivatives were identified. Among these compounds, seven phenolics and three nucleoside derivatives have not been reported yet from<jats:italic> G. elata</jats:italic>.