Titanium and its conventional alloys reveal a high affinity for hydrogen, being capable to absorb up to 60 at.% hydrogen at 600°C, and even higher contents can be alloyed with titanium at lower temperatures. Hydrogen exhibits a low solubility in the low-temperature hexagonal closed-packed (hcp) α phase and a very high solubility (up to 50 at.%) in the high temperature body-centered cubic (bcc) β phase. The presence of hydrogen in the amount exceeding 200 ppm leads to formation of hydrides in α and α + β titanium alloys. While the aforementioned hydrogen behavior within bulk titanium has been well-established and reviewed, this is not the case with titanium thin films. The interpretation of results in these nanosized systems is complicated because the exact determination of the hydrogen concentration is difficult. However, using electrochemical hydrogen loading technique under the proper conditions, the hydrogen concentration can be accurately determined via Faraday’s law. In this study the thermodynamics of the titanium films during hydrogen absorption were investigated by electromotive force (EMF) measurements. Titanium films of different thicknesses were prepared on sapphire substrates in an UHV chamber with a base pressure of 10-8 mbar, using ion beam sputter deposition under Ar-atmosphere at the pressure of 1,5ּ10-4 mbar. The crystal structure was investigated by means of X-Ray diffraction using a Co-Kα radiation. For electrochemical hydrogen loading, the films were covered by a 30 nm thick layer of Pd in order to prevent oxidation and facilitate hydrogen absorption. The samples were step-by-step loaded with hydrogen by electrochemical charging, which was carried out in a mixed electrolyte of phosphoric acid and glycerin (1:2 in volume). An Ag/AgCl (sat.) and Pt wires were used as the reference and the counter electrode, respectively. XRD measurements were performed before and after hydrogenation in order to investigate the effect of hydrogen loading on the films microstructure. The role of varying thicknesses on the main characteristics of hydrogen's absorption behavior, as well as hydrogen-induced microstructural changes in titanium thin films, are discussed in detail.