The absolute configuration of t-butanesulfinamide has been determined as (-)-(S) using three different chiroptical spectroscopic methods, namely, vibrational circular dichroism (VCD), electronic circular dichroism (ECD), and optical rotatory dispersion (ORD). Furthermore, the predominant conformation of this molecule is determined to have S=O and NH2 groups staggered with respect to the three methyl groups and to have amine hydrogens in gauche orientation with respect to S=O. The quality of predictions obtained for vibrational properties, namely, vibrational absorption and VCD, is found to be satisfactory with the B3LYP functional and 6-31G* basis set. However, this basis set is found to be inadequate for obtaining reliable predictions of electronic properties, namely, electronic absorption and ECD, but a larger aug-cc-pVDZ basis set is found to provide satisfactory prediction of electronic properties. t-Butanesulfinamide serves as an example which invalidates the recommendation of using the 6-31G* basis set for molecules that exhibit the same sign for the long-wavelength ECD band and ORD. This molecule also emphasizes the importance of simultaneous investigation of ECD and ORD, and the use of multiple chiroptical spectroscopic methods, for reliable determination of molecular stereochemistry.