AbstractA study of the calcification of the polyvinyl alcohol/polyvinyl pyrrolidone (PVA/PVP) hydrogels during their exposure to a calcium chloride solution or a simulated body fluid has been carried out. On the basis of the experiments, using a two‐compartment permeation cell, the diffusion of calcium ions and their subsequent deposition in the hydrogels were elucidated. Steady‐batch experiments were also performed to further elaborate the deposition pattern and the types of calcium deposits. It was demonstrated that Fick's second law of diffusion can describe the diffusion of calcium ions through PVA/PVP hydrogels at 310 K. The diffusion coefficient was determined to be (4.4 ± 0.1) × 10−10 m2/s and the partition coefficient for the hydrogels was 0.06. Formation of calcium deposits was noticed taking place both on the surface and inside the hydrogels. The deposits formed on the surface have flake morphology, while the deposits inside the hydrogels are more like globular aggregates. Both types of deposits have been characterized as being comprised calcium and hydroxyl ion deficient apatites with chloride ions the most likely substituting species at the hydroxyl sites. © 2007 Wiley Periodicals, Inc. J Biomed Mater Res 2007