An efficient access toward novel tridentate ligands based on 1,7-dipyridinyl-substituted bis-pyrazolo[3,4-b:4′,3′-e]pyridines (BPs) and their usefulness as fluorescent probes for cation detection is reported. The synthesis proceeds by a three-step sequence starting from 2-chloropyridine (1), all reactions were performed using microwave radiation under solvent-free conditions, and an overall yield of up to 63% was obtained. Photophysical properties of three representative 1,7-dipyridinyl-BPs (PBPs, 6a–6c) substituted at position 4 with different donor (D) or acceptor (A) groups were investigated. Compounds exhibited large Stokes shift in different solvents and strong blue light emission in both solution and solid state, and quantum yields were as high as 88% for some of them; thus, a twisted intramolecular charge transfer (TICT) fluorescence mechanism characteristic of the 1,4,7-triaryl-BPs was confirmed. The 4-phenyl-substituted probe (Ph-PBP, 6b) was used successfully in the detection of some metals (Cu2+, Co2+, Ni2+, and Hg2+) by fluorescence quenching phenomena, which could be reversed in the presence of ethylenediamine. This probe showed a greater sensitivity toward Cu2+ in concentrations as low as 26 nM, and in the process of "on–off–on" for this fluorescent molecular switch, only 1 equiv of the analyte was used.