We report the synthesis of C3-symmetric cryptophanes decorated with three aromatic amine groups on the same CTB cap and their interaction with xenon. The relative stereochemistry of these two stereoisomers syn and anti was assessed thanks to the determination of the X-ray structure of an intermediate compound. As previously observed with the tris-aza-cryptophanes analogs anti-1 and syn-2 (J. Org. Chem. 2021, 86, 11, 7648–7658), both compounds anti-5 and syn-6 show a slow in–out exchange dynamics of xenon at 11.7 T. Our work supports the idea that the presence of nitrogen atoms grafted directly onto the cryptophane backbone has a strong impact on the in–out exchange dynamics of xenon whatever their stereochemistry. This result contrasts with the case of other cryptophanes decorated solely with methoxy substituents. Finally, we demonstrate that these new derivatives can be used to design new anti/syn cryptophanes bearing suitable ligands in order to constitute potent 129Xe NMR-based sensors. An example is reported here with the synthesis of the tris-iodo derivatives anti-13 and syn-14 from compounds anti-5 and syn-6.