Self-assembly of rhenium-based nanoscale rectangular prismatic boxes has been achieved in quantitative conversion. The facrhenium corner provided three mutually perpendicular coordination sites and served as a good candidate for the construction of 3-D boxes. These are the first Re-based, neutral, luminescent prisms of M8L2L'(8) type that has been characterized crystallographically. Their luminescent properties and molecular recognition capabilities make these molecular prisms interesting supramolecules.