An HPLC-UV-MS method for simultaneous identification of predominant phenolics and minor nucleoside derivatives in Gastrodia elata 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_max at 267 nm, [M + NH₄]⁺ base peak in positive mode and [M-H]⁻ base peak in negative mode while nucleosides exhibited UV λ_max at 255 nm, [M + H]⁺, [M-H + 2H₂O]⁻ or [M-H + CH₃COOH]⁻. Phenolics conjugates mainly underwent the consecutive loss of gastrodin residue (-268 U) and the combined loss of H₂O and CO₂ 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 G. elata 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 G. elata.