Covering: 2015 to up to 2019 This review presents the recent progress towards elucidating the structures of chiral natural products and applications using vibrational optical activity (VOA) spectroscopy. Vibrational circular dichroism (VCD) and vibrational Raman optical activity (VROA) are two separate branches of VOA spectroscopy, providing independent and complementary structural information. While determining the absolute configuration (AC) of a given natural product is the primary goal, the determination or assessment of major conformations associated with each diastereomer is also a significant part of this enquiry. The latest developments in experimental and computational aspects of VOA spectroscopies and their applications for inferring the AC and predominant conformations of natural products are summarized. The prospects and limitations in the application of VOA spectroscopy to new natural products are summarized.