The dynamic scenario of di-aryls-pyrano-chromenes was investigated using DFT calculations. The symmetry of the chromene scaffold and the presence of twoortho-substituted aryls substituents can generate twosyn/antidiastereoisomers and conformational enantiomers with different rotational barriers. The relative conformations and configurations were derived using NOESY-1D experiments. Depending on the energies related to the conformational exchange, the experimental energy barriers were determined through Dynamic NMR, Dynamic HPLC or kinetic studies. The atropisomeric pairs were resolved in the latter scenario, and their absolute configuration was assigned using the ECD/TD-DFT method.