31P NMR 1D profiling was successfully introduced to measure macroscale mutual-diffusion coefficients ( D m) of phosphate ions in dextran gels. Series of 1D profiles describing the phosphate concentration along cylindrical dextran gels were acquired at different times. These profiles that included over 600 points could be fitted using equations derived from Fick’s law, with D m as the single fitting parameter. Release and penetration profiles were recorded providing two alternative approaches for allowing the determination of D m. The D m values were compared with microscale self-diffusion coefficients ( D s) measured by pulsed field gradient spin echo (PFG-SE) technique. D m values, measured between 25 and 45 °C, were systematically lower than D s. The experimental diffusion time and the associated diffusion length of D s (60 ms, 10 μm) are short compared to those of D m (up to 18 h, 50 mm). These scale differences are considered to be the origin of different D s and D m and provide information relative to the network in these gels.