We describe temperature-induced water release from the complexes of triammonium N,N-diacetatedithiocarbamate (dadtc) with Co(III) (1), Mo(VI) (2) and Pt(II) (3), by the combination of temperature-dependent IR spectroscopy and quantum chemical calculations. Transmission IR spectra show that in the compounds 1 and 2, where water molecules are hydrogen-bonded with complex moieties, water release occurs at about 80 °C. In the compound 3 water most probably exist as non-hydrogen-bonded and remains within the sample above 100 °C. The influence of an inert salt in maintaining the water and consequently bringing up the artefacts in spectra is eliminated by recording the spectra in the internal reflection regime (ATR). Possible interplay of water release from the samples 1 and 2 and samples phase transition is presumed and indicated by the baseline analysis of temperature-dependent transmission IR spectra.