The aim of the present work was to verify the usefulness of dimolybdenum tetrakis(μ-pivalate) and tetrakis(μ-isovalerate) as auxiliary chromophores for determining the absolute configuration of optically active vic-diamines, vic-amino alcohols, α-amino and α-hydroxy acids by means of electronic circular dichroism (ECD). To this end, a series of measurements designed to check the dependence of ECD and UV-Vis spectra on time and concentration was carried out. The experimental results were supported by a separate set of detailed DFT calculations. The results obtained allowed us to determine the most probable structure of dominating chiral complexes formed in situ in solution for all ligands studied.