AbstractChemical investigation of Selaginella chrysocaulos from Northeast India yielded three new (i.e., 1–3) and two known biflavonoids. From Selaginella bryopteris, collected in the southern part of India, one new (11) and eleven known biflavonoids of the amentoflavone‐ and hinokiflavone‐type were isolated and identified. The structures of the compounds were elucidated by 1D‐ and 2D‐NMR spectroscopy, and by mass spectrometry. The absolute configurations of chiral biflavonoids with flavanone subunits (from S. bryopteris) were determined with the aid of circular‐dichroism (CD) spectroscopy. Several very rare or even unprecedented substructures in biflavonoids were found.