Mixtures of Ag(hexanoate) and Ag(palmitate) give thermoreversible gels at very low concentration in toluene. The framework of the gel is composed of the branched nanosized fibers, contrary to the microsized wire precipitates of silver(I) carboxylates. The randomness of mixed-ligand silver(I) carboxylate polymeric chains hinders the crystallization process, resulting in very thin fibrils. This may be a new approach to design and control the properties of materials, which do not have properties involving gels or nanostructures in a conventional process.