The addition of an anionic polymer (HPAM) to a cationic aluminum-based MOF (MIL-96) during the hydrothermal synthesis stage allowed the formation of larger MOF crystals with well-defined crystal habits. Taking advantage of HPAM being a low cost and an environmentally friendly additive, a HPAM-modified MIL-96 (MIL-96-RHPAM2) showed promising particle size growth (from 3.2 µm to 10.4 µm) as well as the ability to control the crystal morphology using this simple modification procedure. Incorporating HPAM into the MIL-96 structure resulted in the introduction of amine (-NH2) functionality, which can form a primary ammonium species (-NH3 + ) that in turn led to improved PFOA adsorption capacity relative to original pristine form, while also promoting higher PFOA affinity compared to AC. Higher concentrations of NaCl in the eluent solvents did not yield enhanced PFOA desorption from both spent adsorbents, MIL-96-RHPAM2 (maximum PFOA desorbed was 77%) and AC (74%), primarily due to the strong PFOA adsorption to both adsorbents.