This paper reports a facile synthesis of decahedral particles of anatase TiO2 dominated by {101} and {001} faces. The decahedral particles has been enhanced by means a microwave-assisted hydrothermal method using TiF4 as a titanium precursor and HF as capping agent to promote oriented growth and formation of {001} faces in only 4 h. The prepared samples were characterized by scanning electron microscopy, high resolution of transmission electron microscopy and X-ray diffraction. The morphology of anatase TiO2 particles is consisted of near-perfect-truncated-bipyramid-shape. Reaction time is a key factor to obtain truncated-bipyramid-shaped particles with sharp and well-defined edges. Reaction times longer than 4 h induce irregular particles. Decahedral anatase TiO2 particles are truncated bypiramid crystals which have eight {101} and two {001} facets at top/bottom surfaces. The average size of decahedral anatase TiO2 particles are similar to 250 nm for the samples obtained without applying the microwave irradiation and similar to 350 nm for reaction 4 h.