Probe diffusion of camphorquinone, thymoquinone, and diacetyl in polymers was studied by the laser-induced holographic grating relaxation (HGR) technique in polymers. The effects of changing the probe size and various parameters of the polymer, such as the molecular weight, chain conformation, and the glass transition temperature, on the probe diffusion coefficient have been investigated. Furthermore, effects of cross-linking and plasticizing the chains of the polymer host on the probe diffusion coefficient were also studied. Temperature-dependent studies show that except for the very low molecular weight poly(methyl methacrylate), all probe diffusion coefficient data above the glass transition temperature fit well to the WLF equation.