Bile salts form aggregates in solution with binding sites that have different properties. The aggregation process is progressive with the increase of the bile salt concentration or ionic strength first forming small primary aggregates with hydrophobic binding sites and then forming larger secondary aggregates with binding sites for hydrophilic molecules. These aggregates are adaptable to the structure of small molecules, accommodating both, very hydrophobic molecules and molecules with hydrophilic moieties. Bile salts, as natural products, can be used in humans. Some bile salts, such as sodium deoxycholate (NaDC, Chart 1), can form self-assembled hydrogels near physiological pH providing the opportunity to immobilize included guest molecules in a viscoelastic material. The formation of gels can be facilitated with the addition of di-or trivalent cations. Bile salts have been used to solubilize in aqueous solutions and in hydrogels a large variety of molecules, such as ionic polymers, photochromic molecules, organic molecules, and carbon nanotubes, and bile salts have been used in advanced material engineering. Based on the self-assembly behavior of NaDC, we explored the ability of NaDC to solubilize and photochemically stabilize a neutral conjugated oligomer, oligo(3-hexylthiophene-co-1,4phenylene) (OTPh, Chart 1). The intrinsic fluorescence of OTPh, the fluorescence of pyrene as an added hydrophobic probe, dynamic light scattering, and rheology experiments were used to characterize the OTPh/NaDC system. This work shows that the self-assembly of OTPh with NaDC in solution and in the gel arises from the interaction of the self-assembled NaDC aggregates with the oligomer, showing that interactions found in solution systems translate to the hydrogel. The oligomer OTPh was chosen as a conjugated polymer model molecule to study the aqueous solubilization with NaDC in solution and hydrogels. This choice was based on the low water solubility of OTPh, and our approach is distinct from previous ones where hydrogels containing ionic water-soluble conjugated polymers or oligomers were formed, or the synthesized conductive polymers formed the hydrogel. The solubilization of OTPh was compared to that of a commercial conjugated polymer poly(3-hexylthiophene) (P3HT, Chart 1), establishing the viability of using NaDC in a supramolecular strategy for the solubilization of neutral conjugated polymers.