Titanium dioxide sols were synthesized by hydrothermal reactions with addition of poly (ethylene glycol) (Mw = 20,000). Using techniques of X-ray diffraction, transmission electron microscopy, dynamic light scattering, and scanning electron microscopy, effect of PEG on the crystallographic properties, particle size, aggregating behavior, and the morphological properties of nanoparticles in the sols were studied. It was found that growth of anatase nanocrystallites was retarded by PEG. Average crystallite size of anatase nanocrystallites first decreased from 20.7 nm to 10.5 nm as the polymer concentration increased from 1 g/L to 3 g/L, and then changed little. Meanwhile, small amount of rutile phases like rutile nanowires, twin crystallites, and the "flowers" appeared continuously when the concentration increased from 3 g/L to 5 g/L. Mono-dispersion was obtained with relatively lower PEG concentration. The observed evolvement was discussed based on the interaction between the polymers and the nanocrystallites with assistance of FTIR. The coverage of polymer chains on surface of nanocrystallites leads to isolated reactors, which benefits the uniform coarsening rate of the nanocrystallites. The synthesized TiO2 sols were utilized in dye sensitized solar cells. Performance parameters of the solar cells were discussed with assistance of dye desorption experiments. The improved dispersion in sols was found to benefit the photovoltaic performance of the cells. (C) 2011 Published by Elsevier Inc.