The thermal evolution of deuterium from thin titanium films, prepared under UHV conditions and deuterated in situ at room temperature, has been studied by means of thermal desorption mass spectrometry (TDMS) and a combination of scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The observed Ti film thickness dependent morphology was found to play a crucial role in the titanium deuteride (TiDy) film formation and its decomposition at elevated temperatures. TDMS heating induced decomposition of fine-grained thin Ti films, of 10 - 20 nm thickness, proceeds at low temperature ( maximum peak temperature T-m about 500 K) and its kinetics is dominated by a low energy desorption (E-D = 0.61 eV) of deuterium from surface and subsurface areas of the Ti film. The origin of this process is discussed as an intermediate decomposition state towards recombinative desorption of molecular deuterium. The TiDy bulk phase decomposition becomes dominant in the kinetics of deuterium evolution from thicker TiDy films. The dominant TDMS peak at approx. T-m = 670 K, attributed to this process, is characterized by E-D = 1.49 eV. (C) 2007 Elsevier B. V. All rights reserved.