The high demand and scarcity of luminescent, photoconductive, and transparent gels necessitate its finding as they are potential components in photonic devices such as solar cell concentrators where optical losses via scattering and reabsorption require to be minimized. In this direction, we have reported highly transparent, blue luminescent as well as photoconductive gels exhibiting the hole mobility of 10 −3 cm 2 /V s at ambient temperature as investigated by the time-of-flight technique. The π-driven self-standing supergels were formed using triazole-modified phenylene-vinylene derivatives as gelators in a nonpolar solvent. Different microscopic studies revealed its entangled network of interwoven fibrilar self-assembly and anisotropic order in the gel state. Supramolecular assembly of xerogels, studied by small-and wide-angle Xray scattering (SAXS/WAXS) suggesting their local columnar hexagonal (Col h ) superstructure, is beneficial for conducting gels. Rheological measurements direct the stiffness and robustness of the organogels. In addition, the gelators were developed as a sensing platform for the ultrasensitive detection of Fe(II) ions at ppb level. 1 H nuclear magnetic resonance (NMR) titrimetric studies revealed that the interaction of the H-atom of triazole units with Fe(II) is responsible for quenching of blue fluorescence. Also, one of the gelators was successfully applied in bio-imaging using the pollen grains of the Hibiscus rosa-sinensis plant.