Adsorption studies of counterions carried by the ruthenium(II) complexes (Bu4N)(2)[Ru(Hdcbpy)(2)(NCS)(2)] (1), (Bu4N)(4)[Ru(dcbpy)(2)(NCS)(2)] (2), and [Ru(H(2)dcbpy)(2)(NCS)(2)] (3) (dcbpy = 2,2'-bipyridyl-4,4'-dicarboxylate, Bu4N = tetrabutylammonium) on TiO2 have been carried out by using thermoanalytical techniques, NMR, and ATR-FTIR spectroscopic methods. The thermogravimetric analysis (TGA) data of the adsorbed complexes 1 and 2 on TiO2 show the presence of 1 and less than or equal to1.3 cations coadsorbed per ruthenium center, respectively. These complexes in the adsorbed state on TiO2 show remarkable stability in air atmospheres at high temperatures up to 180 degreesC. The only process that is observed at lower temperatures is the dehydration, which occurs between 40 and 110 degreesC. At high temperature the processes are deamination of the tetrabutylammonium counterion as well as decarboxylation and decomposition of the complex between 200 and 400 degreesC. The NMR data of the desorbed complexes 1 and 2 from the TiO2 surface show the presence of 1 and less than or equal to1.5 cations, which is in close agreement with the TGA data. Comparative analysis of the ATR-FTIR spectra of complexes 1 and 2 between the free and the adsorbed forms also indicates the presence of 1 and less than or equal to1.5 cations per ruthenium center, respectively.