Sapium sebiferum, an ornamental and bioenergetic plant, is propagated by seed. Its seed coat contains germination inhibitors and takes a long time to stratify for germination. In this study, we discovered that the S. sebiferum seed coat (especially the tegmen) and endospermic cap contained high levels of proanthocyanidins. Seed-coat and endospermic cap removal induced seed germination whereas exogenous application with seed-coat extract or proanthocyanidins significantly inhibited this process, suggesting that proanthocyanidins in the seed coat played a major role in regulating seed germination in S. sebiferum. We further investigated how seed-coat extract affected the expression of the seed-germination-related genes. The results showed that treatment with seed-coat extract upregulated the transcription level of the dormancy-related gene, gibberellins suppressing genes, abscisic acid biosynthesis and signalling genes. Seed-coat extract decreased the transcript levels of abscisic acid catabolic genes, gibberellins biosynthesis genes, reactive oxygen species genes and nitrates-signalling genes. Exogenous application of nordihydroguaiaretic acid, gibberellic acid, hydrogen peroxide and potassium nitrate recovered seed germination in seed-coat-extract supplemented medium. In this study, we highlighted the role of proanthocyanidins, and their interactions with the other germination regulators, in the regulation of seed dormancy in S. sebiferum.