The translational dynamics of poly(ethylene glycol) (PEG) polymers with molecular weights (Mw)varying from 6 × 102 to 5 × 105 were investigated by pulsed field gradient NMR in casein suspensions and in gels induced by acidification, enzyme action, and a combination of both. For molecules with Mw e 1020, the diffusion was only dependent on the casein concentration whatever the molecular weight of the probe or the sample studied. However, for PEG with Mw g 8000, there was strong dependence of diffusion on PEG size and on the casein network structure as revealed by scanning electron microscopy images. The diffusion coefficients of the two largest PEGs were increased after coagulation by amounts that depended on the internal structure of the gel. In addition, the 527 000 g/mol PEG was found to deviate from Gaussian diffusion behavior to greater or lesser extents according to the casein concentration and the sample microstructure. The results are discussed in terms of network rearrangements.