As an investigation for utilization of ascidian tunic carotenoids as a food color additives, we attempted to collect the volatile thermal degradation compounds from ascidian tunic carotenoids. Oxygenate volatile compounds were extracted by simultaneous distillation and extraction/concentration apparatus and analyzed by gas chromatography and mass spectrometery. Total 63 compounds were identified and some of them were caused by thermal degradation. They included 1,3,5-trimethylbenzene, 3,5,5-trimethyl-3-cyclohexen-1-ol, 3,5,5-trimethyl-3-cyclohexen-1-one, 1,1,2,3-tetramethyl-2-cyclohexen-5-ol, 1,1,2,3-tetramethyl-2-cyclohexen-5-one, 2,3,4,4-tetramethyl-6-hydroxy-2-cyclohexene-1-one, 1,2,3,8-tetrahydro-3,3,6-trimethyl-1-naphtol, dihydroacetinidolide, ${\beta}-ionone$, 2-(1,1,5-trimethyl-3-hydroxy-5-cyclohexen-6-yl)-1-tolylethene, 2,6-dimethyl-8-(1,1,5-trimethyl-3-hydroxy-5-cyclohexen-6-yl)-1,3,5-octatriene-7-yne. Proposed mechanism of formation of some compounds as thermal degradation products of ascidian tunic carotenoids are provided.