The irradiation of tumors in radiotherapy requires accurate 3D dosimetry. The Fricke 3D dosimeters, which were considered to be high potential of application in 3D dosimetry, suffer from a reduced temporal integrity of dose distribution caused by Fe3+ ions diffusion. To overcome the drawback, we firstly synthesized a kind of amphiphilic molecules with critical micelle concentration of 0.45 g/L and hydrophile‐lipophile balance value of 10, then prepared multiple emulsions by self‐assembling those molecules in Fricke solution under liquid paraffin, and finally obtained Fricke hydrogel embedded with the multiple emulsions. The diffusion coefficient of Fe3+ ions in the embedded Fricke hydrogel was measured to be 0.17 mm2/h. The hydrogel dosimeter exhibits considerable potential for use in dose verification applications.