Advanced analytical approaches consisting of both LC-LTQ-Orbitrap Fourier transformed (FT)-MS and LC-time-of-flight-(TOF)-MS coupled to solid-phase extraction (SPE) NMR were used to obtain more insight into the complex phenolic composition of tea. On the basis of the combined structural information from (i) accurate mass fragmentation spectra, derived by using LC-Orbitrap FTMS(n), and (ii) proton NMR spectra, derived after LC-TOFMS triggered SPE trapping of selected compounds, 177 phenolic compounds were annotated. Most of these phenolics were glycosylated and acetylated derivatives of flavan-3-ols and flavonols. Principal component analysis based on the relative abundance of the annotated phenolic compounds in 17 commercially available black, green, and white tea products separated the black teas from the green and white teas, with epicatechin-3,5-di-O-gallate and prodelphinidin-O-gallate being among the main discriminators. The results indicate that the combined use of LC-LTQ-Orbitrap FTMS and LC-TOFMS-SPE-NMR leads to a more comprehensive metabolite description and comparison of tea and other plant samples.