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In addition to the repulsive and attractive interaction forces described by Derjaguin–Landau–Verwey–Overbeek (DLVO) theory, many charged colloid systems are stabilized by non-DLVO contributions stemming from specific material attributes. Here, we investigate non-DLVO contributions to the stability of polymer colloids stemming from the intra-particle glass transition temperature ( T g ). Flash nanoprecipitation is used to fabricate nanoparticles (NPs) from a library of polymers and dispersion stability is studied in the presence of both hydrophilic and hydrophobic salts. When adding KCl, stability undergoes a discontinuous decrease as T g increases above room temperature, indicating greater stability of rubbery NPs over glassy NPs. Glassy NPs are also found to interact strongly with hydrophobic phosphonium cations (PR 4 + ), yielding charge inversion and intermediate aggregation while rubbery NPs resist ion adsorption. Differences in the lifetime of ionic structuration within mobile surface layers is presented as a potential mechanism underlying the observed phenomenon.