As a tetrapyridyl compound, nicotinate-terminated 4-arm star-shaped ε-caprolactone oligomer (Tetra-NA-CLO) was synthesized by the esterification reaction of nicotinic acid and hydroxy-terminated 4-arm star-shaped ε-caprolactone oligomer (Tetra-OH-CLO) having the degree of polymerization per one oligocaprolactone chain, n = 5. As disulfonic acids, 1,3-bis(sulfopropoxy)propane (BSP) and 1,6-bis(sulfopropoxy)hexane (BSH) were synthesized by the reactions of 1,3-propanesultone with 1,3-propanediol and 1,6-hexanediol, respectively. A mixture of Tetra-NA-CLO and BSP or BSH became a thermo-reversible organogel in methanol, ethanol, and N,N-dimethylformamide at the concentration not less than 20 wt%. The sol-gel transition temperature of the mixtures was at around 15–20 °C. The 1H NMR analysis of the mixture in a solution revealed a complete ionization of the pyridyl ring by the formation of pyridinium sulfonate moiety. The dried Tetra-NA-CLO/BSP and Tetra-NA-CLO/BSH films had higher crystallinity and melting temperature than that of the dried Tetra-NA-CLO film. The FT-IR analysis of the mixture in a dried solid state revealed that both the ionic and hydrogen-bonding interactions contributed.