The diffusion of ferric ions is an important challenge to limit the application of Fricke gel dosimeters in accurate three-dimensional dose verification of modern radiotherapy. In this work, low-diffusion Fricke gel dosimeters, with a core-shell structure based on spatial confinement, were constructed by utilizing microdroplet ultrarapid freezing and coating technology. Polydimethylsiloxane (PDMS), with its excellent hydrophobicity, was coated on the surface of the pellets. The concentration gradient of the ferric ion was realized through shielding half of a Co-60 photon beam field size, and ion diffusion was measured by both ultraviolet-visible spectrophotometry and magnetic resonance imaging. No diffusion occurred between the core-shell pellets, even at 96 h after irradiation, and the diffusion length at the irradiation boundary was limited to the diameter (2–3 mm) of the pellets. Furthermore, Monte Carlo calculations were conducted to study dosimetric properties of the core-shell dosimeter, which indicated that a PDMS shell hardly affected the performance of the dosimeter.