Hypothesis Diblock copolymer nanoparticles prepared in non-polar solvents that are sterically stabilized but possess ionic functionality from the inclusion of cationic comonomers in the stabilizer shell are known to exhibit complex electrokinetic behavior (Chem. Sci. 9 (2018) 922–934). For example, core-shell nanoparticles with cationic comonomers located solely within the shell layer have lower magnitude electrophoretic mobilities than nanoparticles containing the same cationic comonomers located within the core, and nanoparticles prepared using a minor fraction of steric stabilizer chains containing cationic comonomer repeat units have comparable electrophoretic mobilities to nanoparticles prepared with this cationic comonomer solely located within the core. We hypothesize that these observations can be explained in terms of the strength of the Coulombic interaction between counterions and the nanoparticle interface. Experiments The highly-fluorinated anionic counterion associated with these cationic nanoparticles is studied by 19F nuclear magnetic resonance (NMR) spectroscopy in n-dodecane. This revealed only one type of 19F environment for a soluble macromolecular cation (the oil-soluble steric stabilizer chains used to prepare the nanoparticles), whereas two distinct environments were observed for the sterically-stabilized cationic nanoparticles. Both 19F diffusion NMR and 19F–13C heteronuclear single quantum correlation (HSQC) measurements support the existence of two environments for this counterion. Findings The existence of two distinct 19F environments for the highly-fluorinated anion associated with the sterically-stabilized nanoparticles demonstrates the presence of spectroscopically distinguishable populations of ion pairs and of fully dissociated free anions. 19F NMR spectra recorded for sterically-stabilized nanoparticles with a fully ionic shell (all stabilizer chains containing the cationic comonomer) and those with a partly ionic shell (10% of stabilizer chains containing the cationic comonomer) reveal a higher proportion of dissociated anions in the partly ionic case. This suggests a stronger Coulombic interaction between counterions and the cationic interface when the shell is fully ionic, which accounts for the observed reduction in the magnitude of the electrophoretic mobility.