We investigate the effects of controlled poly(ethylene glycol) (PEG) doping on the behavior of pyrene, rhodamine 6G (R6G), and acrylodan-labeled bovine serum albumin (BSA-Ac) sequestered within tetramethylorthosilicate (TMOS)-derived sol-gel-processed materials. To probe the dipolarity of the local environment within the composite we performed static fluorescence measurements on pyrene as the composites aged. We found that small levels of PEG loading effected significant enhancements in the local dipolarity surrounding the average pyrene molecule. Time-resolved fluorescence anisotropy measurements were used to follow the rotational reorientation dynamics of R6G as the composites aged. As the PEG loading increased, the R6G reorientational mobility increased. Nitrogen adsorption techniques were used to quantify the effects of PEG doping level on the surface area and final xerogel pore features. A large reduction in surface area was observed with PEG doping, but no detectable change in pore size was noted. The effects of PEG doping on a biomolecule were probed by following the time-resolved fluorescence anisotropy decay of BSA-Ac. These results showed that PEG doping resulted in increased biomolecule dynamics relative to that found for a neat, undoped TMOS-derived composites. Together these results show that PEG doping can be used to tune the sol-gel-processed composite dipolarity, alter the mobility of dopants sequestered within the composite, control analyte acessibility to the sensing chemistry, and modulate the internal dynamics within a biodopant.