Herein we present a series of luminescent Tb(III)-probes ([Tb-Ltrp], [Tb-Ltyr], and [Tb-Lphe]) for sensing and discriminating purine nucleoside polyphosphates (NPP) based on a modified DTTA chelator appended to aromatic amino acids (Laa). The optically most effective luminescent [Tb-Ltrp] probe preferentially discriminates the guanine-NPPs over the adenine-NPPs via PeT-based modulation of Tb(III) luminescence within the biological concentration range.