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A novel hydrogel has been synthesized using 2',4',6'-tri(4-pyridyl)pyridine in an acidic water medium. TEM analyses along with rheological experiments explore the supramolecular features of the hydrogel. In vitro and in vivo toxicity studies depict the non-toxic and bio-relevant nature of the pure supramolecular hydrogel and its aqueous solution. This bio-compatible supramolecular hydrogel is used for the synthesis of a DNA-hydrogel with calf thymus DNA. The DNA-hydrogel is intriguing for the effective stabilization of photochemically synthesized silver nanoparticles from Ag(i) under the direct exposure of sunrays. DNA-hydrogel capped Ag-NPs are also bio-compatible. The luminous features of the 2',4',6'-tri(4-pyridyl)pyridine based supramolecular hydrogel, DNA-hydrogel and DNA-hydrogel capped Ag-NPs and their aqueous solutions are explored through fluorescence microscopy and spectral analyses, respectively.