To address the need to develop improved hybrid biopolymer composites, we report on the preparation of composites that contain chitosan and pectin biopolymers with tunable adsorption properties. Binary biopolymer composites were prepared at variable pectin–chitosan composition in a solvent directed synthesis, dimethyl sulfoxide (DMSO) versus water. The materials were characterized using complementary methods (infrared spectroscopy, thermal gravimetric analysis, pH at the point-of-zero charge, and dye-based adsorption isotherms). Pectin and chitosan composites prepared in DMSO yielded a covalent biopolymer framework (CBF), whereas a polyelectrolyte complex (PEC) was formed in water. The materials characterization provided support that cross-linking occurs between amine groups of chitosan and the –COOH groups of pectin. CBF-based composites had a greater uptake of methylene blue (MB) dye over the PEC-based composites. Composites prepared in DMSO were inferred to have secondary adsorption sites for enhanced MB uptake, as evidenced by a monolayer uptake capacity that exceeded the pectin–chitosan PECs by 1.5-fold. This work provides insight on the role of solvent-dependent cross-linking of pectin and chitosan biopolymers. Sonication-assisted reactions in DMSO favor CBFs, while cross-linking in water yields PECs. Herein, composites with tunable structures and variable physicochemical properties are demonstrated by their unique dye adsorption properties in aqueous media.