AbstractThis review focuses on the theoretical background of vibrational circular dichroism (VCD) spectroscopy. Besides discussing the first‐principle approaches of the theoretical evaluation of VCD spectra, practical computational considerations, such as the available electronic structure computational levels and program packages, are summarized. Illustrative examples are shown for the absolute configuration and conformation determination of mid‐sized molecules based on the comparison of calculated end experimental VCD spectra, including the comparison of the performance of different computational levels. The conformational analysis of larger biomolecules, such as carbohydrates, nucleotides, and peptides by VCD spectroscopy, and the theoretical simulation of solvent effects are also discussed. The review is concluded by a short summary of the present stage of the computation of VCD spectra and the expected future direction of theoretical developments. © 2011 John Wiley & Sons, Ltd. WIREs Comput Mol Sci 2011 1 403–425 DOI: 10.1002/wcms.39This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods