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-aminoalcohols, 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, temperature and concentration was carried out. The experimental results were supported by a separate set of detailed DFT calculations. The results obtained allowed to know the most probable structure of dominating chiral complexes formed in situ in solution for all ligands studied.