This paper reports a facile synthesis of anatase TiO(2) nanocrystals with exposed, chemically active {001} facets. The nanocrystals were prepared by digesting electrospun nanofibers consisting of amorphous TiO(2) and poly(vinyl pyrrolidone) with an aqueous acetic acid solution (pH = 1.6), followed by hydrothermal treatment at 150 degrees C for 20 h. The as-obtained nanocrystals exhibited a truncated tetragonal bipyramidal shape with 9.6% of the surface being enclosed by {001} facets. The use of electrospinning is critical to the success of this synthesis as it allows for the generation of very small particles of amorphous TiO(2) to facilitate hydrothermal crystallization, an Ostwald ripening process. The morphology of the nanocrystals had a strong dependence on the pH value of the solution used for hydrothermal treatment. Low pH values tended to eliminate the {001} facets by forming sharp corners while high pH values favored the formation of a rodlike morphology through an oriented attachment mechanism. When acetic acid was replaced by inorganic acids, the TiO(2) nanocrystals further aggregated into larger structures with various morphologies.