This article aims to quantify and differentiate in-situ iron(II) and/or iron(III) in heterogeneous polygalacturonate hydrogels using the 1H‐NMR relaxometry technique. This holds significant importance, for example, in addressing iron-deficiency anemia through the oral administration of iron(II) supplements. The NMR dispersion profiles of the gels exhibited markedly distinct relaxation behaviors corresponding to the different iron oxidation states. At 20 MHz, two primary relaxation mechanisms must be considered: relaxation arising from water molecules confined within the polygalacturonate fiber mesh and paramagnetic relaxation due to iron cations. When iron(III) serves as the cross-linking agent, paramagnetic interaction dominates the relaxation, while with iron(II) as the cross-linker, both mechanisms have to be considered. To distinguish labile from structuring iron, we monitored the evolution of iron concentrations within the gels during successive washes using NMR and atomic absorption spectroscopy. Eventually, a gel containing both iron(II) and iron(III) was analyzed, and successful differentiation between the two cations was achieved. NMR relaxometry demonstrates powerful capabilities in terms of in-situ experiments, rapid results, speciation (iron(II)/iron(III)), and quantification (labile/ bridging iron).