A series of alkynylplatinum(II) complexes of 2,6-bis(N-alkylbenzimidazol-2'-yl)pyridine has been synthesized and characterized by H-1 NMR, IR, FAB mass spectrometry, and elemental analysis; the photophysical properties have also been investigated. All the complexes have been shown to exhibit interesting gelation properties. Scanning electron microscopy (SEM) of the xerogels showed a network of fibrous structures, typical of morphologies of organogels/metallogels. Interestingly, two of the complexes were found to show strong luminescence enhancement upon a gel-to-sol phase transition upon increasing the temperature. This unusual behavior is rarely encountered, as it represents a sharp contrast to that exhibited by other typical thermotropic organogels and metallogels reported so far. Variable-temperature UV-vis and luminescence spectroscopies were performed to probe the gel-to-sol phase transition. Concentration-dependent, variable-temperature, and time-resolved emission studies in dilute benzene solution have also been made to provide further insights into the spectroscopic origin in the Sol forms. A quantitative treatment of the system based on the Birks scheme has been performed.