We describe a general user-friendly platform for fine-tuning the drug release properties of low-molecular-weight hydrogels by a combination of supramolecular co-assembly of complementary molecular structures and controlled photochemical thiol-ene cross-linking.Other critical features such as thermomechanical stability and morphology of the nanostructured hydrogels are also tailored by this approach.Molecular functional gels able to immobilize a large number of solvent molecules have been a subject of study for well over a century. 1 These hierarchical, self-assembled, and viscoelastic materials may be considered to be either hard or soft based on their rheological characteristics, 2 and can be categorized into two major types according to their driving forces for molecular aggregation: chemical gels, 3 based on covalent bonds, and physical gels, 1,4 based on non-covalent bonds. 'Bottom-up' processing of stable and stimuliresponsive gels has allowed their use in important applications (e.g. regenerative medicine, sensors, nanoelectronics, etc.). 5 Nevertheless, the search for a universal platform to fine-tune their functional properties, especially in the case of gels made of low-molecularweight-gelators (LMWGs), continues being a great scientific challenge for the creation of shape-controlled and robust functional soft-materials. 6-8 On the other hand, Sharpless and co-workers introduced, early in this decade, the valuable concept of 'click' chemistry, 9 exemplified by the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC). 10 After the first 'boom' caused by the versatility of the CuAAC, 11 the century-old thiol-ene coupling (TEC) 12 has emerged as a competitive orthogonal strategy for the high-yield synthesis of complex functional networks under mild conditions. 13,14 In this communication, we report the supramolecular co-assembly (SMCA) of complementary structures followed by controlled TEC as a new user-friendly strategy for fine-tuning the drug release kinetics of self-assembled hydrogels made of LMWGs. In addition, its effect on the sol-to-gel transition temperature (T gel ) and morphology of the materials is also described.The hydrogelation ability of LMW hydrogelator dibenzoyl-L-cystine (1) at very low concentrations (0.2 wt%) was already noted in 1892 15 and revisited by Menger and Caran in the late 90's. 16 The gelation phenomenon is driven here by a favorable backbone orientation (CH 2 -S-S-CH 2 dihedral angle $87 to 99 ) enhanced by cooperative hydrogen-bonding and p-p stacking interactions (Fig. 1). Inspired by our previous studies directed towards the mechanical stabilization of organogels via CuAAC, 17 pseudocomplementary compounds 2-4 were synthesized by incorporation of terminal alkene units. 18 In contrast to other LMWGs, 19 the simple co-assembly process of LMWG 1 at 0.2 wt% in water with the corresponding alkene-containing analogues 2, 3 or 4 (under optimized molar ratio 1 : (2-4) ¼ 10 : 1) did not improve the mechanical strength of the fragile original hydrogel. 18 The stability of the h...