A two-component gel resulting from the amphiphilic cationic surfactant cetylpyridinium chloride (CPC) in the presence of a structure-forming bola-amphiphilic additive 6-aminocaproic acid (6-ACA) was realized and investigated. At a critical 6 wt % of 1:1 CPC:6-ACA, the yellow colored gel resulted from a 3:1 v/v CHCl3:H2O critical binary solvent composition. The mixed amphiphilic system formed a 1:1 complex with a binding constant similar to 0.83 X 10(4) M-1. Phase evolution and mechanism of gelation in the mixed CPC:6-ACA.system was unraveled upon investigating the gel microstructure, based on spectroscopic, microscopic, and small-angle X-ray scattering (SAXS) investigations. The gel assembled as a lamellar organization, maintaining a loosely interdigitated bilayer structure of CPC and 6-ACA molecules through predominant charge transfer, H-bonding, and hydrophobic and intercomplex interactions. The SAXS pattern indicated a semicrystalline form to be the stable phase with alternating crystalline and amorphous layers; a novel mode of gelation with a widely disparate semicrystalline form of the lamellar gel was thus indicated, where the lamellar structure was deduced from the interplanar spacings. A transition from low viscosity reverse micellar solution to a yellow rigid gel upon aging was thus comprehended. The mixed amphiphile in varying polarity organic solvents in the presence of water indicated the nonconducive nature of gelation in very highly polar solvents, methanol, and DMF or, in very low polarity solvents, such as, cyclohexane and carbon tetrachloride.