Single-walled carbon-nanotubes (SWNTs) exhibit unique electronic, optical, and mechanical properties; however, a narrow availability of chirally pure (single electronic structure) material can limit effective integration within novel devices and schemes. This work focuses on understanding, modeling, and advancing methodology used to generate preparative quantities of single-chirality SWNT: the iterative adsorption/desorption of SWNT from aqueous surfactant suspensions to/from hydrogel microspheres. Commercially available hydrogel microspheres (Sephacryl S200) were sorted by radius and exposed to SWNT, affording a direct correlation between microsphere surface area and quantity of SWNT adsorbed using differential absorbance spectroscopy. This relationship elucidates a SWNT/gel purification scheme interaction mechanism exclusively involving the gel surface. High-concentration surfactant was used to elute SWNT from the gel with desorption efficiencies dependent on both SWNT chirality and hydrogel microsphere radius, ranging from 25–45%. A thermodynamic model for SWNT desorption that accounts for hydrogel microsphere curvature effects is presented and suggests that (when compared with experimental data) SWNT with greater than ∼41% of their length adsorbed to a hydrogel surface bind irreversibly, while others are desorbed in the presence of high-concentration surfactant. These findings inspired the generation and application of mechanically fractured hydrogel microspheres (exhibiting greater surface area) for use as SWNT purification media in per-iteration quantities far less than traditional gels. A 10-iteration SWNT purification procedure demonstrated a marked improvement in process efficiency, as mechanically fractured gels afford a 10-fold reduction in gel-media use (the major expense of the process) while yielding equivalent SWNT purification.