Thearubigins are the most abundant group of phenolic pigments found in black tea, accounting for an estimated 60-70% of the solids in a typical black tea infusion. Fifty years ago the term thearubigins was first introduced and to date the chemical nature of the thearubigins remains largely unresolved, if not mysterious, despite numerous attempts made to clarify their structure. Thearubigins isolated from 15 commercial black teas have been analyzed using a strategy combining standard chemical characterization along with a series of modern complementary mass spectrometry techniques, including MALDI-TOF-MS, FTICR-MS, LC/TOF-MS and LC/MS/MS. Fifteen molecular formulas have been matched to constituents of fresh tea leaf that have survived processing and 21 to dimeric transformation products such as theasinensins, theaflavins, theaflavates, theanaphthoquinones, theacitrins and oolongtheanins, which were further confirmed by ESI MS/MS. MALDI-TOF-MS data revealed an average of 5000 additional thearubigin components in the mass range between m/z 1000 to 2100 clearly defining the molecular weight range of the thearubigin fraction. Six selected samples have for the first time been analyzed by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). FT-ICR-MS data revealed the presence of a maximum of 9428 peaks in the mass range 300 to 1000 m/z and molecular formulas were assigned to 1517 of them. Data interpretation strategies developed for petrolomics studies (van Krevelen and Kendrick analyses) have for the first time been applied to black tea thearubigins and a novel interpretation protocol has been developed to refine these procedures for the investigation of complex mixtures, leading to a novel hypothesis for the formation and structure of the black tea thearubigins named oxidative cascade hypothesis.