Five oligochitosans with increasing degrees of polymerization (DPs), i.e., from chitotriose to chitoheptaose, were examined to clarify the structure-bioactivity relationship between the DPs of oligochitosans and their effects on the isoflavone metabolites, total phenolic and flavonoid contents (TPC and TFC, respectively), and antioxidant activity of soybean ( Glycine max) seeds during germination. Oligochitosans of different DPs exhibited varying influences on the TPC, TFC, and antioxidant activities of soybean seeds. Chitohexaose exerted a strong effect and significantly increased the aforementioned parameters in soybean seeds 72 h after germination. Genistin, malonylgenistin, and genistein were the main isoflavones found, and the genistin and genistein contents were significantly enhanced by 67.32% and 131.38%, respectively, after chitohexaose treatment. Several critical genes involved in the isoflavone biosynthesis (i.e., PAL, CHS, CHI, IFS) of soybeans treated with and without chitohexaose were analyzed, and results suggested that chitohexaose application could dramatically stimulate the transcription of these genes.