Metal-organic polyhedra represent a unique class of functional molecular containers that display interesting molecular recognition properties and fascinating reactivity reminiscent of the natural enzymes. By incorporating a triphenylamine moiety as a bright blue emitter, a robust cerium-based tetrahedron was developed as a luminescent detector of nitronyl nitroxide (PTIO), a specific spin-labeling nitric oxide (NO) trapper. The tetrahedron encapsulates molecules of NO and PTIO within the cavity to prompt the spin-trapping reaction and transforms the normal EPR responses into a more sensitively luminescent signaling system with the limit of detection improved to 5 nM. Twelve-fold amide groups are also functionalized within the tetrahedron to modify the hydrophilic/lipophilic environment, ensuring the successful application of biological imaging in living cells.