High purity, spherical anatase nanocrystals were prepared by a modified sol−gel method. Mixing of anhydrous TiCl₄ with ethanol at about 0 °C yielded a yellowish sol that was transformed into phase-pure anatase of 7.7 nm in size after baking at 87 °C for 3 days. This synthesis route eliminates the presence of fine seeds of the nanoscale brookite phase that frequently occurs in low-temperature formation reactions and also significantly retards the phase transformation to rutile at high temperatures. Heating the as-is 7.7 nm anatase for 2 h at temperatures up to 600 °C leads to an increase in grain size of the anatase nanoparticles to 32 nm. By varying the calcination time from 2 to 48 h at 300 °C, the particle size could be controlled between 12 and 15.3 nm. The grain growth kinetics of anatase nanoparticles was found to follow the equation, D² − D₀² = k₀t^me^(-E_a/RT) with a time exponent m = 0.286(±9) and an activation energy of E_a = 32 ± 2 kJ·mol^-1. Thermogravimetric analysis in combination with infrared and X-ray photoemission spectroscopies has shown the anatase nanocrystals at different sizes to be composed of an interior anatase lattice with surfaces that are hydrogen-bonded to a wide set of energetically nonequivalent groups. With a decrease in particle size, the anatase lattice volume contracts, while the surface hydration increases. The removal of the surface hydration layers causes coarsening of the nanoparticles.