We have developed a method for analysing vitamin E using ultra-performance convergence chromatography with a chromatographic runtime of 5.5 min. A well-resolved chromatogram with excellent precision in retention time revealed seven vitamin E components in the palm oil derived tocotrienol-rich fraction. The major vitamin E components were α-tocopherol, α-tocotrienol, γ-tocotrienol and δ-tocotrienol whereas the minor vitamin E components were α-tocomonoenol, β-tocotrienol and an unreported trace component. The new component was positively identified by high-resolution mass spectrometry as 2-methyl-2(4',8',12'-trimethyltrideca-7',11'-dienyl)5,7,8-trimethylchroman-6-ol or α-tocodienol.