Enantiopure cryptophane derivatives 1 and 2, possessing linkers of different nature (ethylenedioxy and propylenedioxy) connecting the two cyclotribenzylenes (CTB) units, were separated by HPLC using chiral stationary phases. Xray crystallographic structures of the four enantiomers (+)-1, (-)-1, (+)-2, and (-)-2 have been obtained, allowing the unambiguous determination of their absolute configuration (AC) in the solid state. The chiroptical properties of compounds 1 and 2 were determined from polarimetry, electronic circular dichroism (ECD), vibrational circular dichroism (VCD), and Raman optical activity (ROA) experiments and were compared to those of cryptophane-A (3) derivative. VCD, ROA and ECD spectra of 1 and 2 were calculated by density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations, respectively, to confirm the AC of the cryptophane derivatives in solution. The (+)-PP and (-)-MM configurations were established for compounds 1 and 2 in chloroform solution, as already reported for the two enantiomers of 3. This result is in agreement with the X-ray structures of the two enantiomers of 1 and 2.