In a previous paper, it was reported that the preferred crystalline orientation of TiO2 transferred significantly from (110) face in starting TiO2 powders to (101) and (111) faces in TiO2 coating deposited on both stainless steel and glass substrates by plasma-sprayedJ. Mater. Sci. Lett. 17 (1998) 1747]. An understanding of the change in the preferred orientations has remained elusive. In this communication, the valence electron structure of TiO2 is established on the basis of Pauling's nature of the chemical bond and the change in the preferred orientations is explained satisfactory.