Polymeric assemblies are used in many biomaterials applications, ranging from drug-bearing nanoparticles to macroscopic scaffolds. Control over their biodegradation rates is usually achieved through synthetic modification of their molecular structure. As a simpler alternative, we exploit the associative phase separation in mixtures of bioderived surfactants and polyelectrolytes. The gel fiber scaffolds are formed via phase inversion, using a homologous series of fatty acid salts-sodium caprate (NaC10), laurate (NaC12), and myristate (NaC14), and a water-soluble chitosan derivative, N-[(2-hydroxy-3-trimethylammonium)propyl] chitosan chloride (HTCC). Their dissolution times are modulated through the selection of the fatty acid molecule and vary in a predictable manner from minutes (for NaC10-HTCC), to hours (for NaC12-HTCC), to days (for NaC14-HTCC). These variations are linked to differences in surfactant-polyelectrolyte binding strength and scale with the equilibrium binding constants of their mixtures. These fibers were found to be both cytocompatible and cell-adhesive using neural stem/progenitor cells, suggesting their potential for utility in biomedical applications.